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.

Electron-conduction mechanism and specific heat above transition temperature in LaFeAsO and BaFe2As2 superconductors

The ionization energy theory is used to calculate the evolution of the resistivity and specific heat curves with respect to different doping elements in the recently discovered superconducting pnictide materials. Electron-conduction mechanism in the pnictides above the structural transition temperature is explained unambiguously, which is also consistent with other strongly correlated materials, such as cuprates, manganites, titanates and magnetic semiconductors.

High-rate, low-temperature synthesis of composition controlled hydrogenated amorphous silicon carbide films in low-frequency inductively coupled plasmas

It is commonly believed that in order to synthesize high-quality hydrogenated amorphous silicon carbide (a-Si1-xCx : H) films at competitive deposition rates it is necessary to operate plasma discharges at high power regimes and with heavy hydrogen dilution. Here we report on the fabrication of hydrogenated amorphous silicon carbide films with different carbon contents x (ranging from 0.09 to 0.71) at high deposition rates using inductively coupled plasma (ICP) chemical vapour deposition with no hydrogen dilution and at relatively low power densities (∼0.025 W cm -3) as compared with existing reports. The film growth rate R d peaks at x = 0.09 and x = 0.71, and equals 18 nm min-1 and 17 nm min-1, respectively, which is higher than other existing reports on the fabrication of a-Si1-xCx : H films. The extra carbon atoms for carbon-rich a-Si1-xCx : H samples are incorporated via diamond-like sp3 C-C bonding as deduced by Fourier transform infrared absorption and Raman spectroscopy analyses. The specimens feature a large optical band gap, with the maximum of 3.74 eV obtained at x = 0.71. All the a-Si1-xCx : H samples exhibit low-temperature (77 K) photoluminescence (PL), whereas only the carbon-rich a-Si1-xCx : H samples (x ≥ 0.55) exhibit room-temperature (300 K) PL. Such behaviour is explained by the static disorder model. High film quality in our work can be attributed to the high efficiency of the custom-designed ICP reactor to create reactive radical species required for the film growth. This technique can be used for a broader range of material systems where precise compositional control is required. © 2008 IOP Publishing Ltd.

Influence of hydrogen dilution on the growth of nanocrystalline silicon carbide films by low-frequency inductively coupled plasma chemical vapor deposition

Nanocrystalline silicon carbide (nc-SiC) films are prepared by low-frequency inductively coupled plasma chemical vapor deposition from feedstock gases silane and methane diluted with hydrogen at a substrate temperature of 500 °C. The effect of different hydrogen dilution ratios X [hydrogen flow (sccm) / silane + methane flow (sccm)] on the growth of nc-SiC films is investigated by X-ray diffraction, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). At a low hydrogen dilution ratio X, cubic silicon carbide is the main crystal phase; whereas at a high hydrogen dilution ratio X, hexagonal silicon carbide is the main crystal phase. The SiC crystal phase transformation may be explained by the different surface mobility of reactive Si-based and C-based radicals deposited at different hydrogen dilution ratios X. The FTIR and XPS analyses show that the Si-C bonds are the main bonds in the films and elemental composition of SiC is nearly stoichiometric with almost equal share of silicon and carbon atoms.

Self-assembled low-dimensional nanomaterials via low-temperature plasma processing

Examples of successful fabrication of low-dimensional semiconducting nanomaterials in the Integrated Plasma-Aided Nanofabrication Facility are shown. Self-assembled size-uniform ZnO nanoparticles, ultra-high-aspect ratio Si nanowires, vertically aligned cadmium sulfide nanostructures, and quarternary semiconducting SiCAlN nanomaterial have been synthesized using inductively coupled plasma-assisted RF magnetron sputtering deposition. The observed increase in crystallinity and growth rates of the nanostructures are explained by using a model of plasma-enhanced adatom surface diffusion under conditions of local energy exchange between the ion flux and the growth surface. Issues related to plasma-based growth of low-dimensional semiconducting nanomaterials are discussed as well. © 2007 Elsevier B.V. All rights reserved.

Electron/ion energy loss to discharge walls revised : a case study in low-temperature, thermally nonequilibrium plasmas

Reliable calculations of the electron/ion energy losses in low-pressure thermally nonequilibrium low-temperature plasmas are indispensable for predictive modeling related to numerous applications of such discharges. The commonly used simplified approaches to calculation of electron/ion energy losses to the chamber walls use a number of simplifying assumptions that often do not account for the details of the prevailing electron energy distribution function (EEDF) and overestimate the contributions of the electron losses to the walls. By direct measurements of the EEDF and careful calculation of contributions of the plasma electrons in low-pressure inductively coupled plasmas, it is shown that the actual losses of kinetic energy of the electrons and ions strongly depend on the EEDF. It is revealed that the overestimates of the total electron/ion energy losses to the walls caused by improper assumptions about the prevailing EEDF and about the ability of the electrons to pass through the repulsive potential of the wall may lead to significant overestimates that are typically in the range between 9 and 32%. These results are particularly important for the development of power-saving strategies for operation of low-temperature, low-pressure gas discharges in diverse applications that require reasonably low power densities. © 2008 American Institute of Physics.

Behavior of the electron temperature in nonuniform complex plasmas

The response of complex ionized gas systems to the presence of nonuniform distribution of charged grains is investigated using a kinetic model. Contrary to an existing view that the electron temperature inevitably increases in the grain-occupied region because of enhanced ionization to compensate for the electrons lost to the grains, it is shown that this happens only when the ionizing electric field increases in the electron depleted region. The results for two typical plasma systems suggest that when the ionizing electric field depends on the spatially averaged electron density, the electron temperature in the grain containing region can actually decrease.

Low-temperature PECVD of nanodevice-Grade nc-3C-SiC

In this work, we report a plasma-based synthesis of nanodevice-grade nc-3C-SiC films, with very high growth rates (7-9 nm min-1) at low and ULSI technology-compatible process temperatures (400-550 °C), featuring: (i) high nanocrystalline fraction (67% at 550 °C); (ii) good chemical purity; (iii) excellent stoichiometry throughout the entire film; (iv) wide optical band gap (3.22-3.71 eV); (v) refractive index close to that of single-crystalline 3C-SiC, and; (vi) clear, uniform, and defect-free Si-SiC interface. The counter-intuitive low SiC hydrogenation in a H2-rich plasma process is explained by hydrogen atom desorption-mediated crystallization.

Growth kinetics of carbon nanowall-like structures in low-temperature plasmas

The results of a hybrid numerical simulation of the growth kinetics of carbon nanowall-like nanostructures in the plasma and neutral gas synthesis processes are presented. The low-temperature plasma-based process was found to have a significant advantage over the purely neutral flux deposition in providing the uniform size distribution of the nanostructures. It is shown that the nanowall width uniformity is the best (square deviations not exceeding 1.05) in high-density plasmas of 3.0× 1018 m-3, worsens in lower-density plasmas (up to 1.5 in 1.0× 1017 m-3 plasmas), and is the worst (up to 1.9) in the neutral gas-based process. This effect has been attributed to the focusing of ion fluxes by irregular electric field in the vicinity of plasma-grown nanostructures on substrate biased with -20 V potential, and differences in the two-dimensional adatom diffusion fluxes in the plasma and neutral gas-based processes. The results of our numerical simulations are consistent with the available experimental reports on the effect of the plasma process parameters on the sizes and shapes of relevant nanostructures.

Electrostatic nanoparticle filter for atomic scale fabrication in low-temperature plasmas

The means of reducing nanoparticle contamination in the synthesis of carbon nanostructures in reactive Ar + H2 + CH4 plasmas are studied. It is shown that by combining the electrostatic filtering and thermophoretic manipulation of nanoparticles, one can significantly improve the quality of carbon nanopatterns. By increasing the substrate heating power, one can increase the size of deposited nanoparticles and eventually achieve nanoparticle-free nanoassemblies. This approach is generic and is applicable to other reactive plasma-aided nanofabrication processes.

Low-temperature assembly of ordered carbon nanotip arrays in low-frequency, high-density inductively coupled plasmas

High-density inductively coupled plasma (ICP)-assisted self-assembly of the ordered arrays of various carbon nanostructures (NS) for the electron field emission applications is reported. Carbon-based nano-particles, nanotips, and pyramid-like structures, with the controllable shape, ordering, and areal density are grown under remarkably low process temperatures (260-350 °C) and pressures (below 0.1 Torr), on the same Ni-based catalyst layers, in a DC bias-controlled floating temperature regime. A high degree of positional and directional ordering, elevated sp2 content, and a well-structured graphitic morphology are achieved without the use of pre-patterned or externally heated substrates.

Nanoparticle manipulation in the near-substrate areas of low-temperature, high-density rf plasmas

Manipulation of a single nanoparticle in the near-substrate areas of high-density plasmas of low-temperature glow discharges is studied. It is shown that the nanoparticles can be efficiently manipulated by the thermophoretic force controlled by external heating of the substrate stage. Particle deposition onto or repulsion from nanostructured carbon surfaces critically depends on the values of the neutral gas temperature gradient in the near-substrate areas, which is directly measured in situ in different heating regimes by originally developed temperature gradient probe. The measured values of the near-surface temperature gradient are used in the numerical model of nanoparticle dynamics in a variable-length presheath. Specific conditions enabling the nanoparticle to overcome the repulsive potential and deposit on the substrate during the discharge operation are investigated. The results are relevant to fabrication of various nanostructured films employing structural incorporation of the plasma-grown nanoparticles, in particular, to nanoparticle deposition in the plasma-enhanced chemical-vapor deposition of carbon nanostructures in hydrocarbon-based plasmas.

Low-temperature growth of large area, vertically aligned carbon nanotubes for field emission applications

Large area, highly uniform vertically aligned carbon nanotips (VACNTP) and other nanostructures have been grown on silicon (100) substrates with Ni catalyst in the low-temperature, low-frequency, high-density inductively coupled plasmas (ICP) of methane-hydrogen-argon gas mixtures. The control strategies for the morphology, crystalline structure and chemical states of the resulting nanostructures by varying the growth conditions are proposed. XRD and Roman analyses confirm that the nanotips are well graphitized, which is favorable for the field emission applications.

SiC-like phase and room-temperature photoluminescence of low-k SiOCH films

Carbon-doped hydrogenated silicon oxide (SiOCH) low-k films have been prepared using 13.56 MHz discharge in trimethylsilane (3MS) - oxygen gas mixtures at 3, 4, and 5 Torr sustained with RF power densities 1.3 - 2.6 W/cm2. The atomic structure of the SiOCH films appears to be a mixture the amorphous SiO2-like and the partially polycrystalline SiC-like phases. Results of the infra-red spectroscopy reflect the increment in the volume fraction of the SiC-like phase from 0.22 - 0.28 to 0.36 - 0.39 as the RF power increment. Steady-state near-UV laser-excited (364 nm wavelength, 40±2 mW) photoluminescence (PL) has been studied at room temperatures in the visible (1.8 eV - 3.1 eV) subrange of photon spectrum. Two main bands of the PL signal (at the photon energies of 2.5 - 2.6 eV and 2.8 - 2.9 eV) are observed. Intensities of the both bands are changed monotonically with RF power, whereas the bandwidth of ∼0.1 eV remains almost invariable. It is likely that the above lines are dumped by the non-radiative recombination involving E1-like centres in the amorphous-nanocrystalline SiC-like phases. Such explanation of the PL intensity dependences on the RF power density is supported by results of experimental studies of defect states spectrum in bandgap of the SiOCH films.

Self-organization and dynamics of nanoparticles in chemically active plasmas for low-temperature deposition of silicon and carbon-based nanostructured films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C 2H2), and octafluorocyclobutane (c-C4F 8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.