Propriedades estruturais e ópticas de filmes finos a-C:H:CI obtidos por deposição à vapor químico assistido por plasma e deposição e implantação iônica por imersão em plasma

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Caracterização de Filmes a-C:H:Cl e a-C:H:Si:Cl produzidos por deposição à vapor químico assistido por plasma (PECVD) e deposição e implantação iônica por imersão em plasma (PIIID)

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Formation and electron field emission of graphene films grown by hot filament chemical vapor deposition

Graphene films with different structures were catalytically grown on the silicon substrate pre-deposited with a gold film by hot filament chemical vapor deposition under different conditions, where methane, hydrogen and nitrogen were used as the reactive gases. The morphological and compositional properties of graphene films were studied using advanced instruments including field emission scanning electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the structure and composition of graphene films are changed with the variation of the growth conditions. According to the theory related to thermodynamics, the formation of graphene films was theoretically analyzed and the results indicate that the formation of graphene films is related to the fast incorporation and precipitation of carbon. The electron field emission (EFE) properties of graphene films were studied in a high vacuum system of ∼10-6 Pa and the EFE results show that the turn-on field is in a range of 5.2-5.64 V μm-1 and the maximum current density is about 63 μ A cm-2 at the field of 7.7 V μm-1. These results are important to control the structure of graphene films and have the potential applications of graphene in various nanodevices.

Nanoscale plasma chemistry enables fast, size-selective nanotube nucleation

The possibility of fast, narrow-size/chirality nucleation of thin single-walled carbon nanotubes (SWCNTs) at low, device-tolerant process temperatures in a plasma-enhanced chemical vapor deposition (CVD) is demonstrated using multiphase, multiscale numerical experiments. These effects are due to the unique nanoscale reactive plasma chemistry (NRPC) on the surfaces and within Au catalyst nanoparticles. The computed three-dimensional process parameter maps link the nanotube incubation times and the relative differences between the incubation times of SWCNTs of different sizes/chiralities to the main plasma- and precursor gas-specific parameters and explain recent experimental observations. It is shown that the unique NRPC leads not only to much faster nucleation of thin nanotubes at much lower process temperatures, but also to better selectivity between the incubation times of SWCNTs with different sizes and chiralities, compared to thermal CVD. These results are used to propose a time-programmed kinetic approach based on fast-responding plasmas which control the size-selective, narrow-chirality nucleation and growth of thin SWCNTs. This approach is generic and can be used for other nanostructure and materials systems.

Control of density of self-organized carbon nanotube arrays by catalyst pretreatment through plasma immersion ion implantation

A simple and effective method of controlling the growth of vertically aligned carbon nanotube arrays in a lowerature plasma is presented. Ni catalyst was pretreated by plasma immersion ion implantation prior to the nanotube growth by plasma-enhanced chemical vapor deposition. Both the size distribution and the areal density of the catalyst nanoparticles decrease due to the ion-surface interactions. Consequently, the resulting size distribution of the vertically aligned carbon nanotubes is reduced to 50 ∼ 100 nm and the areal density is lowered (by a factor of ten) to 10 8 cm -2, which is significantly different from the very-high-density carbon nanotube forests commonly produced by thermal chemical vapor deposition. The efficiency of this pretreatment is compared with the existing techniques such as neutral gas annealing and plasma etching. These results are highly relevant to the development of the next-generation nanoelectronic and optoelectronic devices that require effective control of the density of nanotube arrays.

Heating and plasma sheath effects in low-temperature, plasma-assisted growth of carbon nanofibers

Plasma sheath, nanostructure growth, and thermal models are used to describe carbon nanofiber (CNF) growth and heating in a low-temperature plasma. It is found that when the H2 partial pressure is increased, H atom recombination and H ion neutralization are the main mechanisms responsible for energy release on the catalyst surface. Numerical results also show that process parameters such as the substrate potential, electron temperature and number density mainly affect the CNF growth rate and plasma heating at low catalyst temperatures. In contrast, gas pressure, ion temperature, and the C2H2:H2 supply ratio affect the CNF growth at all temperatures. It is shown that plasma-related processes substantially increase the catalyst particle temperature, in comparison to the substrate and the substrate-holding platform temperatures.

Plasma-assisted self-organized growth of uniform carbon nanocone arrays

The self-organized growth of uniform carbon nanocone arrays using low-temperature non-equilibrium Ar + H 2 + CH 4 plasma-enhanced chemical vapor deposition (PECVD) is studied. The experiment shows that size-, shape-, and position-uniform carbon nanocone arrays can develop even from non-uniformly fragmented discontinuous nickel catalyst films. A three-stage scenario is proposed where the primary nanocones grow on large catalyst particles during the first stage, and the secondary nanocones are formed between the primary ones at the second stage. Finally, plasma-related effects lead to preferential growth of the secondary nanocones and eventually a uniform nanopattern is formed. This does not happen in a CVD process with the same gas feedstock and surface temperature. The proposed three-stage growth scenario is supported by the numerical experiment which generates nanocone arrays very similar to the experimentally synthesized nanopatterns. The self-organization process is explained in terms of re-distribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array. Our results suggest that plasma-related self-organization effects can significantly reduce the non-uniformity of carbon nanostructure arrays which commonly arises from imperfections in fragmented Ni-based catalyst films.

Integrated plasma-aided nanofabrication facility: Operation, parameters, and assembly of quantum structures and functional nanomaterials

The development, operation, and applications of two configurations of an integrated plasma-aided nanofabrication facility (IPANF) comprising low-frequency inductively coupled plasma-assisted, low-pressure, multiple-target RF magnetron sputtering plasma source, are reported. The two configurations of the plasma source have different arrangements of the RF inductive coil: a conventional external flat spiral "pancake" coil and an in-house developed internal antenna comprising two orthogonal RF current sheets. The internal antenna configuration generates a "unidirectional" RF current that deeply penetrates into the plasma bulk and results in an excellent uniformity of the plasma over large areas and volumes. The IPANF has been employed for various applications, including low-temperature plasma-enhanced chemical vapor deposition of vertically aligned single-crystalline carbon nanotips, growth of ultra-high aspect ratio semiconductor nanowires, assembly of optoelectronically important Si, SiC, and Al1-xInxN quantum dots, and plasma-based synthesis of bioactive hydroxyapatite for orthopedic implants.

Graphitization of nanocrystalline carbon microcoils synthesized by catalytic chemical vapor deposition

Graphitization, a common process involving the transformation of metastable nongraphitic carbon into graphite is one of the major present-day challenges for micro- and nanocarbons due to their unique structural character and highly unusual thermal activation. Here we report on the successful graphitization of nanocrystalline carbon microcoils prepared by catalytic chemical vapor deposition and post-treated in argon atmosphere at temperatures ∼2500 °C for 2 h. The morphology, microstructure, and thermal properties of the carbon microcoils are examined in detail. The graphitization mechanism is discussed by invoking a model of structural transformation of the carbon microcoils. The results reveal that after graphitization the carbon microcoils are prominently purified and feature a clear helical morphology, as well as a more regular and ordered microstructure. The interlayer spacing of the carbon microcoils decreases from 0.36 to 0.34 nm, whereas the mean crystal sizes in the c - and a -directions increase from 1.64 to 2.04 nm and from 3.86 to 7.21 nm, respectively. Thermal treatment also substantially improves the antioxidation properties of the microcoils by lifting the oxidation onset temperature from 550 to 672 °C. This process may be suitable for other nongraphitic micro- and nanomaterials.

Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (≤1000 K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

Inductively coupled Ar/CH₄/H₂plasmas for low-temperature deposition of ordered carbon nanostructures

The study of inductively coupled Ar/CH 4/H 2 plasmas in the plasma enhanced chemical vapor deposition (PECVD) of self-assembled carbon nanostructures (CN) was presented. A spatially averaged (global) discharge model was developed to study the densities and fluxes of the radical neutrals and charged species, the effective electron temperature, and methane conversion factors under various conditions. It was found that the deposited cation fluxes in the PECVD of CNs generally exceed those of the radical neutrals. The agreement with the optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS) was also derived through numerical results.

Microscopic ion fluxes in plasma-aided nanofabrication of ordered carbon nanotip structures

Three-dimensional topography of microscopic ion fluxes in the reactive hydrocarbon-based plasma-aided nanofabrication of ordered arrays of vertically aligned single-crystalline carbon nanotip microemitter structures is simulated by using a Monte Carlo technique. The individual ion trajectories are computed by integrating the ion equations of motion in the electrostatic field created by a biased nanostructured substrate. It is shown that the ion flux focusing onto carbon nanotips is more efficient under the conditions of low potential drop Us across the near-substrate plasma sheath. Under low- Us conditions, the ion current density onto the surface of individual nanotips is higher for higher-aspect-ratio nanotips and can exceed the mean ion current density onto the entire nanopattern in up to approximately five times. This effect becomes less pronounced with increasing the substrate bias, with the mean relative enhancement of the ion current density ξi not exceeding ∼1.7. The value of ξi is higher in denser plasmas and behaves differently with the electron temperature Te depending on the substrate bias. When the substrate bias is low, ξi decreases with Te, with the opposite tendency under higher- Us conditions. The results are relevant to the plasma-enhanced chemical-vapor deposition of ordered large-area nanopatterns of vertically aligned carbon nanotips, nanofibers, and nanopyramidal microemitter structures for flat-panel display applications. © 2005 American Institute of Physics.

Low-temperature plasma-assisted growth of optically transparent, highly oriented nanocrystalline AlN

Optically transparent, highly oriented nanocrystalline AlN(002) films have been synthesized using a hybrid plasma enhanced chemical vapor deposition and plasma-assisted radio frequency (rf) magnetron sputtering process in reactive Ar+ N2 and Ar+ N2 + H2 gas mixtures at a low Si(111)/glass substrate temperature of 350 °C. The process conditions, such as the sputtering pressure, rf power, substrate temperature, and N2 concentration were optimized to achieve the desired structural, compositional, and optical characteristics. X-ray diffractometry reveals the formation of highly c -oriented AlN films at a sputtering pressure of 0.8 Pa. Field emission scanning electron microscopy suggests the uniform distribution of AlN grains over large surface areas and also the existence of highly oriented in the (002) direction columnar structures of a typical length ∼100-500 nm with an aspect ratio of ∼7-15. X-ray photoelectron and energy dispersive x-ray spectroscopy suggest that films deposited at a rf power of 400 W feature a chemically pure and near stoichiometric AlN. The bonding states of the AlN films have been confirmed by Raman and Fourier transform infrared spectroscopy showing strong E2 (high) and E1 transverse optical phonon modes. Hydrogenated AlN films feature an excellent optical transmittance of ∼80% in the visible region of the spectrum, promising for advanced optical applications.

Nanofabrication of single-crystalline flat-panel display microemitters : a plasma-building unit approach

This contribution is focused on plasma-enhanced chemical vapor deposition systems and their unique features that make them particularly attractive for nanofabrication of flat panel display microemitter arrays based on ordered patterns of single-crystalline carbon nanotip structures. The fundamentals of the plasma-based nanofabrication of carbon nanotips and some other important nanofilms and nanostructures are examined. Specific features, challenges, and potential benefits of using the plasma-based systems for relevant nanofabrication processes are analyzed within the framework of the "plasma-building unit" approach that builds up on extensive experimental data on plasma diagnostics and nanofilm/nanostructure characterization, and numerical simulation of the species composition in the ionized gas phase (multicomponent fluid models), ion dynamics and interaction with ordered carbon nanotip patterns, and ab initio computations of chemical structure of single crystalline carbon nanotips. This generic approach is also applicable for nanoscale assembly of various carbon nanostructures, semiconductor quantum dot structures, and nano-crystalline bioceramics. Special attention is paid to most efficient control strategies of the main plasma-generated building units both in the ionized gas phase and on nanostructured deposition surfaces. The issues of tailoring the reactive plasma environments and development of versatile plasma nanofabrication facilities are also discussed.

Low-frequency, high-density, inductively coupled plasma sources : operation and applications

Operation regimes, plasma parameters, and applications of the low-frequency (∼500 kHz) inductively coupled plasma (ICP) sources with a planar external coil are investigated. It is shown that highly uniform, high-density (ne∼9×1012 cm-3) plasmas can be produced in low-pressure argon discharges with moderate rf powers. The low-frequency ICP sources operate in either electrostatic (E) or electromagnetic (H) regimes in a wide pressure range without any Faraday shield or an external multipolar magnetic confinement, and exhibit high power transfer efficiency, and low circuit loss. In the H mode, the ICP features high level of uniformity over large processing areas and volumes, low electron temperatures, and plasma potentials. The low-density, highly uniform over the cross-section, plasmas with high electron temperatures and plasma and sheath potentials are characteristic to the electrostatic regime. Both operation regimes offer great potential for various plasma processing applications. As examples, the efficiency of the low-frequency ICP for steel nitriding and plasma-enhanced chemical vapor deposition of hydrogenated diamond-like carbon (DLC) films, is demonstrated. It appears possible to achieve very high nitriding rates and dramatically increase micro-hardness and wear resistance of the AISI 304 stainless steel. It is also shown that the deposition rates and mechanical properties of the DLC films can be efficiently controlled by selecting the discharge operating regime.