Thermodynamics approach of the formation of Ni catalyst particles for carbon nanotubes growth

Size-dependent thermodynamic parameters, such as Gibbs free energy, enthalpy and entropy, for the transition of a Ni nanofilm to catalyst particles for subsequent carbon nanotube growth have been explored. In this investigation, we consider the derived equations of the size-dependent melting temperature of nanosolids based on our previous works. Using this thermodynamic approach, it is found that the diameter of Ni particles is 3 times greater than the thickness of the original film. From the critical and stable sizes of transformed Ni nanoparticles, a minimum film thickness for transformation of film to nanoparticles was obtained. Our predictions are in good agreement with experimental results.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

Ultrafast dynamics of delocalized and localized electrons in carbon nanotubes

We report on the dynamics of the dielectric function of single-wall carbon nanotubes in the 10-30 THz frequency range after ultrafast laser excitation. The absence of a distinct free-carrier response is attributed to the photogeneration of strongly bound excitons in the tubes with large energy gaps. We find a feature of enhanced transmission caused by the blocking of optical transitions in small-gap tubes. The rapid decay of a featureless background with pronounced dichroism is associated with the increased absorption of spatially localized charge carriers before thermalization is completed.     

Microscopic growth mechanisms for carbon and boron-nitride nanotubes

Received: 27 November 1998 / Accepted: 18 December 1998     

Growth of carbon nanotubes using nanocrystalline carbon catalyst

The basic growth of carbon nanotubes (CNTs) involves dissociation of hydrocarbon molecules over a metal layer as a catalyst. Generally, the metals used for the catalyst include nickel, cobalt, gold, iron, platinum, and palladium. However, the metal catalyst used with CNTs could have a harmful influence on the electrical properties of electronic devices. Therefore, we propose the use of nanocrystalline carbon (nc-C) as the catalyst for the growth of CNTs. We used a nc-C catalyst layer deposited by the closed-field unbalanced magnetron (CFUBM) sputtering method, and CNTs were grown by the hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment and acetylene gas (C₂H₂) as a carbon source. The CNTs were grown on the nc-C layers pretreated with a variation of the pretreatment time. The characteristics of the pretreated nc-C layers and the grown CNTs were investigated by field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) measurements. Also, the structural variation of the pretreated nc-C layers was investigated by Raman measurement. We used the nc-C catalyst without metal, and we confirmed that our CNTs were composed with only carbon elements through an EDS measurement. Also, the pretreatment time was attributed to the growth of CNTs.     

Electron-hole plasma excitations in single-walled carbon nanotubes

We study theoretically the π-electron-hole plasma excitations in single-walled metallic carbon nanotubes within the framework of the classical electrodynamics. The π-electrons and holes of the nanotubes are described by means of the two-fluid hydrodynamic theory. Numerical results show that the low-energy excitations are in qualitative agreement with low-frequency excitations (π plasmon) in experimental observations in the case where the π-electron and hole effective masses are nearly equal.     

X-ray radiation of laser plasma of carbon nanotubes

Experimental results on the spatial distribution of X-ray radiation of the plasma generated by nanosecond laser radiation incident on a target made of carbon nanotubes are presented and compared with the results obtained for solid-state magnesium targets.     

Aspects of crystal growth within carbon nanotubes

The comparative crystallisation and HRTEM imaging properties of simple binary halides formed by the alkali iodides MI (M = Li, K, Na, Rb and Cs) within single walled carbon nanotubes (SWNTs) are described. The most common structure type observed within SWNTs is the rocksalt archetype, although CsI was observed to form both bcc and rocksalt structure types. In SWNTs forming in the 1.2–1.6 nm diameter range, all of the incorporated halides showed preferred orientation, with the 〈100〉 growth direction predominating for rocksalt-type packing and 〈112〉 so far observed exclusively for bcc packing. Crystals with dimensions spanning 2–6 atomic layers thickness in projection invariably exhibited lattice expansions that were attributed predominantly to a net reduction in coordination at the crystal-carbon interface. The crystallisation behaviour of UCl₄–KCl and AgI–AgCl eutectic melts was compared in carbon nanotubes of different diameters and a pronounced ordering influence over the normally glassy melts was observed in narrower capillaries. HgI₂ crystallised within nanotubes with ultra-narrow (i.e., 0.8 nm) capillaries were observed to form helical 2 ×1 layer crystals. To cite this article: J. Sloan et al., C. R. Physique 4 (2003).     

Selective growth of individual multiwalled carbon nanotubes

Growth of individual, vertically aligned multiwalled carbon nanotubes (VACNT) on patterned Si wafers using dc plasma-enhanced CVD is described. The selective growth of individual VACNT within larger holes etched in Si is demonstrated for the first time.     

Low ambient temperature CVD growth of carbon nanotubes

We show that good quality single-walled and multi-walled carbon nanotubes can be grown on CMOS-compatible metal electrodes at ambient room temperature using highly localised catalyst heating at nanostructured electrodes. The method is relatively straightforward and allows considerable flexibility in the kinds of devices that can be fabricated as well as allowing CVD nanotube growth to take place in the close vicinity of temperature-sensitive materials and devices. PACS 81.07.-b; 81.07.De     

Electric field aligned growth of single-walled carbon nanotubes

Electric field aligned, single-walled carbon nanotubes are grown between electrodes using thermal chemical vapour deposition (CVD) of methane. The growth occurs on a thin film layered catalyst of aluminium, iron and molybdenum patterned on top of electrodes. The nanotubes bridge 10 μm sized electrode gaps and have a typical diameter of less than 2 nm as measured by Raman spectroscopy and atomic force microscopy. We present electrical transport measurements on a directly grown nanotube which shows p-type semiconducting behaviour.     

Zinc oxide catalyzed growth of single-walled carbon nanotubes

We demonstrate that zinc oxide can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency by a chemical vapor deposition process. The zinc oxide nanocatalysts, prepared using a diblock copolymer templating method and characterized by atomic force microscopy (AFM), were uniformly spaced over a large deposition area with an average diameter of 1.7 nm and narrow size distribution. Dense and uniform SWNTs films with high quality were obtained by using a zinc oxide catalyst, as characterized by scanning electron microscopy (SEM), Raman spectroscopy, AFM, and high-resolution transmission electron microscopy (HRTEM).     

Catalytic production of carbon nanotubes by vapor phase growth method using tungsten-containing organic compound

We report the production of carbon nanotubes of high purity by a vapor phase growth method using a catalytic reaction of a tungsten-containing organic compound (C₁₄H₁₀O₇W) and acetylene mixture. The products were multi-walled carbon nanotubes with hollow cores. Transmission electron microscopy investigation revealed that the graphitic layers at the inner region were highly crystallized but the graphitic layers at the outer region had a wavy structure. We have demonstrated the effective production of carbon nanotubes using a tungsten-based catalyst. PACS 81.07.De; 61.46.+w; 68.37.-d     

Metallic nanoparticles on plasma treated carbon nanotubes: Nanohybrids

Multi-wall carbon nanotubes (MWCNTs) were decorated with metal clusters by thermal evaporation. Transmission electron microscopy (TEM) shows that the nature and extent of metal coverage can be varied by plasma treating the MWCNT surface. The metal clusters on oxygen plasma treated arc-discharge MWCNTs have a more dense distribution than the clusters evaporated on as-synthesized arc-discharge MWCNTs. In contrast, the plasma treatment did not affect the cluster distribution on CVD MWCNTs. Analyses of the valence band and the core levels by X-ray photoelectron spectroscopy suggest poor charge transfer between gold clusters and MWCNTs; on the contrary suggest good charge transfer between Ni clusters and MWCNTs.     

Reduced carbon solubility in Fe nanoclusters and implications for the growth of single-walled carbon nanotubes

Fe nanoclusters are becoming the standard catalysts for growing single-walled carbon nanotubes via chemical vapor decomposition. Contrary to the Gibbs-Thompson model, we find that the reduction of the catalyst size requires an increase of the minimum temperature necessary for the growth. We address this phenomenon in terms of solubility of C in Fe nanoclusters and, by using first-principles calculations, we devise a simple model to predict the behavior of the phases competing for stability in Fe-C nanoclusters at low temperature. We show that, as a function of particle size, there are three scenarios compatible with steady state growth, limited growth, and no growth of single-walled carbon nanotubes, corresponding to unaffected, reduced, and no solubility of C in the particles.     

Prediction of optimum catalysts and cocatalysts for chemical growth of carbon nanotubes

A practically important problem of growth of different kinds of carbon nanotubes from nanodrops of a metal catalyst oversaturated by carbon is solved by finding cocatalysts that provide a minimum nucleation energy for the critical nucleus of a nanotube. For pure catalysts, it turns out that the optimum is achieved using atoms of well-known elements of the iron group, which have a minimum energy of the van-der-Waals interaction with graphene islands and a certain energy E _Me-C of the interaction with a carbon atom. It is also possible to obtain even more effective catalysts by finding an appropriate ratio of the components by the trial and error method. In particular, the experimentally found combinations nickel-yttrium and cobalt-molybdenum are among the most effective ones.     

Position-selective growth of vertically aligned carbon nanotubes for application of electronic-measuring nanoprobes

Position-selective growth of carbon nanotubes (CNTs) and vertically aligned CNTs (VACNTs) on patterned metal electrodes have been prepared by thermal chemical vapor deposition (TCVD) and DC plasma enhanced chemical vapor deposition (PECVD). We propose newly a position-controlling method of CNTs by controlling not only a position of Ni as catalysts but also the morphology of Mo as underlayers for the catalysts. The position-selective growth of CNTs was achieved at the edges of the patterned metal by TCVD. The morphologies of the Mo underlayer at the selected area were rough and porous. No CNTs grew on smooth Mo surfaces. The minimum width of selectively grown CNTs, ca. 2.6 μm, was approximately one-eightieth of the patterned metal, 200 μm. VACNTs were synthesized by a PECVD method, however, the VACNTs grew up all over the patterned metal. The Ni catalysts formed into fine particles on rough surfaces of the Mo underlayer. Then the selective growth was achieved by Ni fine particles formed only at the edges of the metal pattern. The results of PECVD suggest that the plasma promoted the Ni catalysts to become fine particles on smooth surfaces of Mo. Conclusively a position-controlling method of CNTs was demonstrated in the optimum conditions of the TCVD.     

Surface growth of single-walled carbon nanotubes from ruthenium nanoparticles

In this paper, we report that ruthenium is an active and efficient catalyst for growth of single-walled carbon nanotubes (SWNTs) by a chemical vapor deposition (CVD) process for the first time. High density random and horizontally superlong well-oriented SWNTs on substrate can be fabricated via CH₄ or EtOH as carbon source under suitable conditions. Scanning and transition electron microscopy investigations, Raman spectroscopy and atomic force microscopy measurements show the tubular structure, the high crystallinity, and the properties of the grown nanotubes. The results show that the SWNTs from ruthenium have better structural uniformity with less defects and provides an alternative catalyst for SWNTs growth. The successful growth of SWNTs by Ru catalyst provides new experimental information for understanding the growth mechanism of SWNTs, which may be helpful for their controllable synthesis.