Controlled fabrication of patterned lateral porous alumina membranes.

Confined lateral alumina templates are fabricated with different pore sizes by changing the acid electrolyte and the anodization voltage. The control of the number of pore rows down to one dimension is also achieved, by controlling the thickness of the starting aluminum film as well as the anodization voltage. We observe that the mechanism of pore formation in the lateral regime is very similar to that in the classical vertical situation.

Density control of electrodeposited Ni nanoparticles/nanowires inside porous anodic alumina templates by an exponential anodization voltage decrease.

Porous alumina templates have been fabricated by applying an exponential voltage decrease at the end of the anodization process. The time constant η of the exponential voltage function has been used to control the average thickness and the thickness distribution of the barrier layer at the bottom of the pores of the alumina structure. Depending on the η value, the thickness distribution of the barrier layer can be made very uniform or highly scattered, which allows us to subsequently fine tune the electrodeposition yield of nickel nanoparticles/nanowires at low voltage. As an illustration, the pore filling percentage with Ni has been varied, in a totally reproducible manner, between ∼3 and 100%. Combined with the ability to vary the pore diameter and repetition step over ∼2 orders of magnitude (by varying the anodization voltage and electrolyte type), the control of the pore filling percentage with metal particles/nanowires could bring novel approaches for the organization of nano-objects.

Localized CVD growth of oriented and individual carbon nanotubes from nanoscaled dots prepared by lithographic sequences.

Using a combination of top-down lithographic techniques, isolated, individual and oriented multi-wall carbon nanotubes (MWNTs) were grown on nickel or iron nanoscaled dots. In the first step of the process, micron-sized catalytic metallic dots (either iron or nickel) were prepared using UV lithography. MWNTs were then synthesized from these catalysts using a direct current plasma-assistance and hot-filament-enhanced chemical vapor deposition (CVD) reactor. Samples were characterized by means of scanning electron microscopy. It turns out that the splitting up of the micron-sized dot is favored in the iron case and that the surface diffusion of the metal is enhanced using ammonia in the gaseous mixture during the CVD process. The results are discussed giving arguments for the understanding of the MWNT growth mechanism. In a second step, a focused ion beam (FIB) procedure is carried out in order to reduce the initial dot size down to submicronic scale and subsequently to grow one single MWNT per dot. It is found that nickel is most appropriate to control the size of the dot. Dots of size 200 nm +/- 40 nm are then required to grow individual MWNTs.

A nucleation and growth model of vertically-oriented carbon nanofibers or nanotubes by plasma-enhanced catalytic chemical vapor deposition.

Carbon nanofibers are grown by direct current and hot filaments-activated catalytic chemical vapor deposition while varying the power of the hot filaments. Observations of these carbon nanofibers vertically oriented on a SiO2 (8 nm thick)/Si(100) substrate covered with Co nanoparticles (10-15 nm particle size) by Scanning Electron and Transmission Electron Microscopies show the presence of a graphitic "nest" either on the surface of the substrate or at the end of the specific nanofiber that does not encapsulate the catalytic particle. Strictly in our conditions, the activation by hot filaments is required to grow nanofibers with a C2H2 - H2 gas mixture, as large amounts of amorphous carbon cover the surface of the substrate without using hot filaments. From these observations as well as data of the literature, it is proposed that the nucleation of carbon nanofibers occurs through a complex process involving several steps: carbon concentration gradient starting from the catalytic carbon decomposition and diffusion from the surface of the catalytic nanoparticles exposed to the activated gas and promoted by energetic ionic species of the gas phase; subsequent graphitic condensation of a "nest" at the interface of the Co particle and substrate. The large concentration of highly reactive hydrogen radicals mainly provided by activation with hot filaments precludes further spreading out of this interfacial carbon nest over the entire surface of the substrate and thus selectively orientates the growth towards the condensation of graphene over facets that are perpendicular to the surface. Carbon nanofibers can then be grown within the well-known Vapor-Liquid-Solid process. Thus the effect of energetic ions and highly reactive neutrals like atomic hydrogen in the preferential etching of carbon on the edge of graphene shells and on the broadening of the carbon nanofiber is underlined.

Ni and Ni/Pt filling inside multiwalled carbon nanotubes.

Multiwalled carbon nanotubes are grown by microwave plasma chemical vapor deposition with CH4 and H2 as precursor gases. Ni and Ni/Pt electroplated layers are used as catalysts for the synthesis of the tubes. We observe that a very efficient filling of the tubes takes place with Ni. In some cases Ni/Pt filling is also observed inside the tubes. High-resolution transmission electron microscopy (HRTEM) studies, coupled with energy-dispersive X-ray analyses of the tubes, indicate Ni nanorods with a highly symmetrical cylindrical structure. The diameter of the cylindrical nanorods is on the order of 40 nm, and their length is 660 nm. The nano area diffraction pattern of the nanorods reveals the cubic structure of nickel, and electron diffraction spots corresponding to (111), (200), (220) planes are evident. The lattice constant of Ni measured from the diffraction spots was found to be 0.347 +/- 0.0013 nm. This should be compared with 0.352 nm, the value of "a" in bulk Ni. The decrease in the lattice constant may be due to the strain experienced inside the tubes. Raman spectroscopy shows the typical signature of the tangential breathing mode present in the tubes at 1580 cm-1 that shifts to a new position when the C12 is replaced by 13C. The shift, however, is too small and is difficult to explain on the basis of mass difference. HRTEM experiments indicate the presence of Ni3C in the samples dominantly in the interfacial region.