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.

Plasma-controlled metal catalyst saturation and the initial stage of carbon nanostructure array growth

The kinetics of the nucleation and growth of carbon nanotube and nanocone arrays on Ni catalyst nanoparticles on a silicon surface exposed to a low-temperature plasma are investigated numerically, using a complex model that includes surface diffusion and ion motion equations. It is found that the degree of ionization of the carbon flux strongly affects the kinetics of nanotube and nanocone nucleation on partially saturated catalyst patterns. The use of highly ionized carbon flux allows formation of a nanotube array with a very narrow height distribution of half-width 7 nm. Similar results are obtained for carbon nanocone arrays, with an even narrower height distribution, using a highly ionized carbon flux. As the deposition time increases, nanostructure arrays develop without widening the height distribution when the flux ionization degree is high, in contrast to the fairly broad nanostructure height distributions obtained when the degree of ionization is low.

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.

Nonlinear effects of ionization on surface waves on a plasma-metal interface

Nonlinear effects associated with density modulation caused by wave-induced ionization in magnetized plasmas were studied. The ionizing surface waves propagate at the interface between the plasma and a metallic surface. It is shown that the ionization nonlinearity can be important for typical experimental conditions.

Standing surface waves in a dust-contaminated large-area planar plasma source

The effect of charged particulates or dusts on surface wave produced microwave discharges is studied. The frequencies of the standing electromagnetic eigenmodes of large-area flat plasmas are calculated. The dusts absorb a significant amount of the plasma electrons and can lead to a modification of the electromagnetic field structure in the discharge by shifting the originally excited operating mode out of resonance. For certain given proportions of dusts, mode conversion is found to be possible. The power loss in the discharge is also increased because of dust-specific dissipations, leading to a decrease of the operating mode quality factor.

Thermophoretic control of building units in the plasma-assisted deposition of nanostructured carbon films

The role of the plasma-grown nanoparticles in the plasma-enhanced chemical vapor deposition (PECVD) of the nanostructured carbon-based films was investigated. The samples were grown in the low-pressure rf plasmas of CH 4+H2+Ar gas mixtures. The enhanced deposition of the building units from the gas phase was found to support the formation of polymorphous nanostructured carbon films. The results reveal the crucial role played by the thermophoretic force in controlling the deposition of the plasma-grown fine particles.

Deterministic shape control in plasma-aided nanotip assembly

The possibility of deterministic plasma-assisted reshaping of capped cylindrical seed nanotips by manipulating the plasma parameter-dependent sheath width is shown. Multiscale hybrid gas phase/solid surface numerical experiments reveal that under the wide-sheath conditions the nanotips widen at the base and when the sheath is narrow, they sharpen up. By combining the wide- and narrow-sheath stages in a single process, it turns out possible to synthesize wide-base nanotips with long- and narrow-apex spikes, ideal for electron microemitter applications. This plasma-based approach is generic and can be applied to a larger number of multipurpose nanoassemblies. © 2005 American Institute of Physics.

Visible photoluminescence from plasma-synthesized SiO 2-buffered SiN x films : effect of film thickness and annealing temperature

The effect of the film thickness and postannealing temperature on visible photoluminescence (PL) from Si Nx films synthesized by plasma-assisted radio frequency magnetron sputtering on Si O2 buffer layers is investigated. It is shown that strong visible PL is achieved at annealing temperatures above 650 °C. The optimum annealing temperature for the maximum PL yield strongly depends on the film thickness and varies from 800 to 1200°C. A comparative composition-structure-property analysis reveals that the PL intensity is directly related to the content of the Si-O and Si-N bonds in the Si Nx films. Therefore, sufficient oxidation and moderate nitridation of Si Nx Si O2 films during the plasma-based growth process are crucial for a strong PL yield. Excessively high annealing temperatures lead to weakened Si-N bonds in thinner Si Nx films, which eventually results in a lower PL intensity.

Customizing electron confinement in plasma-assembled Si/AlN nanodots for solar cell applications

Size-uniform Si nanodots (NDs) are synthesized on an AlN buffer layer at low Si(111) substrate temperatures using inductively coupled plasma-assisted magnetron sputtering deposition. High-resolution electron microscopy reveals that the sizes of the Si NDs range from 9 to 30 nm. Room-temperature photoluminescence (PL) spectra indicate that the energy peak shifts from 738 to 778 nm with increasing the ND size. In this system, the quantum confinement effect is fairly strong even for relatively large (up to 25 nm in diameter) NDs, which is promising for the development of the next-generation all-Si tandem solar cells capable of effectively capturing sunlight photons with the energies between 1.7 (infrared: large NDs) and 3.4 eV (ultraviolet: small NDs). The strength of the resulting electron confinement in the Si/AlN ND system is evaluated and justified by analyzing the measured PL spectra using the ionization energy theory approximation.

Thermodynamical and plasma-driven kinetic growth of high-aspect-ratio nanostructures : effect of hydrogen termination

The results of studies on the growth of high-aspect nanostructures in low-temperature non-equilibrium plasmas of reactive gas mixtures with or without hydrogen are presented. The results suggest that the hydrogen in the reactive plasma strongly affects the length of the nanostructures. This phenomenon is explained in terms of selective hydrogen passivation of the lateral and top surfaces of the surface-supported nanostructures. The theoretical model describes the effect of the atomic hydrogen passivation on the nanostructure shape and predicts the critical hydrogen coverage of the lateral surfaces necessary to achieve the nanostructure growth with the pre-determined shape. Our results demonstrate that the use of a strongly non-equilibrium plasma is very effective in significantly improving the shape control of quasi-one-dimensional single-crystalline nanostructures.

Extremely non-equilibrium synthesis of luminescent zinc oxide nanoparticles through energetic ion condensation in a dense plasma focus device

Luminescent ZnO nanoparticles have been synthesized on silicon and quartz substrates under extremely non-equilibrium conditions of energetic ion condensation during the post-focus phase in a dense plasma focus (DPF) device. Ar+, O+, Zn+ and ZnO+ ions are generated as a result of interaction of hot and dense argon plasma focus with the surfaces of ZnO pellets placed at the anode. It is found that the sizes, structural and photoluminescence (PL) properties of the ZnO nanoparticles appear to be quite different on Si(1 0 0) and quartz substrates. The results of x-ray diffractometry and atomic force microscopy show that the ZnO nanoparticles are crystalline and range in size from 5-7 nm on Si(1 0 0) substrates to 10-38 nm on quartz substrates. Room-temperature PL studies reveal strong peaks related to excitonic bands and defects for the ZnO nanoparticles deposited on Si (1 0 0), whereas the excitonic bands are not excited in the quartz substrate case. Raman studies indicate the presence of E2 (high) mode for ZnO nanoparticles deposited on Si(1 0 0).

Diffusivity of adatoms on plasma-exposed surfaces determined from the ionization energy approximation and ionic polarizability

Microscopic surface diffusivity theory based on atomic ionization energy concept is developed to explain the variations of the atomic and displacement polarizations with respect to the surface diffusion activation energy of adatoms in the process of self-assembly of quantum dots on plasma-exposed surfaces. These polarizations are derived classically, while the atomic polarization is quantized to obtain the microscopic atomic polarizability. The surface diffusivity equation is derived as a function of the ionization energy. The results of this work can be used to fine-tune the delivery rates of different adatoms onto nanostructure growth surfaces and optimize the low-temperature plasma based nanoscale synthesis processes.

High-rate, room temperature plasma-enhanced deposition of aluminum-doped zinc oxide nanofilms for solar cell applications

A custom-designed inductively coupled plasma (ICP)-assisted radio-frequency magnetron sputtering deposition system has been employed to synthesize aluminium-doped zinc oxide (ZnO:Al) nanofilms on glass substrates at room temperature. The effects of film thickness and ZnO target (partially covered by Al chips) power on the structural, electrical and optical properties of the ZnO:Al nanofilms are studied. A high growth rate (∼41 nm/min), low electrical sheet resistance (as low as 30 Ω/□) and high optical transparency (>80%) over the visible spectrum has been achieved at a film thickness of ∼615 nm and ZnO target power of 150 W. The synthesis of ZnO:Al nanofilms at room temperature and with high growth rates is attributed to the unique features of the ICP-assisted radio-frequency magnetron sputtering deposition approach. The results are relevant to the development of photovoltaic thin-film solar cells and flat panel displays.

Plasma heating effects in catalyzed growth of carbon nanofibres

A theoretical model describing the plasma-assisted growth of carbon nanofibres (CNFs) that accounts for the nanostructure heating by ion and etching gas fluxes from the plasma is developed. Using the model, it is shown that fluxes from the plasma environment can substantially increase the temperature of the catalyst nanoparticle located on the top of the CNF with respect to the substrate temperature. The difference between the catalyst and the substrate temperatures depends on the substrate width, the length of the CNF, the neutral gas density and temperature as well as the densities of the ions and atoms of the etching gas. In addition to the heating of the nanostructure, the ions and etching gas atoms from the ionized gas environment also strongly affect the CNF growth rates. Due to ion bombardment, the CNF growth rates in plasma enhanced chemical vapour deposition may be much higher than the rates in similar neutral gas-based thermal processes. The CNF growth model, which accounts for the nanostructure heating by the plasma-generated species, provides the growth rates that are in better agreement with the available experimental data on CNF growth than the models in which the heating effects are ignored.

A model of a large-area planar plasma producer based on surface wave propagation in a plasma-metal structure with a dielectric sheath

A theoretical model of a large-area planar plasma producer based on surface wave (SW) propagation in a plasma-metal structure with a dielectric sheath is presented. The SW which produces and sustains the microwave gas discharge in the planar structure propagates along an external magnetic field and possesses an eigenfrequency within the range between electron cyclotron and electron plasma frequencies. The spatial distributions of the produced plasma density, electromagnetic fields, energy flow density, phase velocity and reverse skin depth of the SW are obtained analytically and numerically.