Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

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.

Modes of nanotube growth in plasmas and reasons for single-walled structure

The conditions for carbon nanotube synthesis in the bulk of arc discharges and on plasma-exposed solid surfaces are compared to reveal the main distinguishing features of the growth kinetics and explain the striking difference between the growth of the nanotubes in both cases. It is shown that this difference is due to very different exposure of the discharge-synthesized and surface-bound nanotubes to ion fluxes, with the ratio of the ion fluxes collected per nanotube in the two cases reaching up to six orders of magnitude. Depending on the plasma parameters and the sizes of the nanotubes and metal catalyst particles, four distinct growth modes of the nanotubes in the plasma bulk have been identified. These results shed light on why single-walled carbon nanotube growth is more favourable in the bulk of arc plasmas rather than on plasma-exposed surfaces.

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.

Nanopowder management and plasma parameters in nanofabrication of low-dimensional quantum structures in reactive silane-based plasmas

Management of nanopowder and reactive plasma parameters in a low-pressure RF glow discharge in silane is studied. It is shown that the discharge control parameters and reactor volume can be adjusted to ensure lower abundance of nanopowders, which is one of the requirements of the plasma-assisted fabrication of low-dimensional quantum nanostructures. The results are relevant to micro- and nanomanufacturing technologies employing low-pressure glow discharge plasmas of silane-based gas mixtures.

Bistability and hysteresis in inductively coupled plasmas

The transition between the two stable operation regimes (E and H discharge modes) in inductively coupled argon plasmas has been studied experimentally and theoretically. Analogy with other physical phenomena exhibiting hysteresis has been drawn. Analysis of power balance, electromagnetic field, plasma parameters, densities of the excited states, and optical emission spectra shows that the hysteresis may be due to nonlinearities associated with step-wise ionization through excited states of the argon atoms.

Turning points, power transfer, and frequency response of mode transitions in RF plasmas

Turning points for transitions between the electrostatic and electromagnetic discharge modes in low-frequency (∼ 500 kHz) inductively coupled plasmas have been identified and cross-referenced using time-resolved measurements of the plasma optical emission intensities, RF coil current, and ion saturation current collected by a single RF-compensated Langmuir probe. This enables one to monitor the variation of the plasma parameters, power transfer efficiency, which accompany the discharge hysteresis. The excitation conditions for the pure and hybrid modes in the plasma are considered, and the possibility of the TMmnl → TEm'n'l' transitions at higher frequencies are discussed.

Surface waves in strongly irradiated dusty plasmas

High-frequency surface waves at the interface between two dusty plasmas subject to radiation are considered. Ultraviolet radiation with energy flux larger than the photoelectric work function of the dust surface causes photoemission of electrons. The dust charge and the overall charge balance of the plasma are thus modified. The dispersion properties of the surface waves are investigated for three parameter regimes distinguished by the charging mechanisms in the two plasmas. It is shown that photoemission can significantly affect the plasma and the surface waves.

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.

Parameters and equilibrium profiles for large-area surface-wave sustained plasmas

The equilibrium profiles of the plasma parameters of large-area if discharges in a finite-length metal-shielded dielectric cylinder are computed using a two-dimensional fluid code. The rf power is coupled to the plasma through edge-localized surface waves traveling in the azimuthal direction along the plasma edge. It is shown that self-consistent accounting for axial plasma diffusion and radial nonuniformity of the electron temperature can explain the frequently reported deviations of experimentally measured radial density profiles from that of the conventional linear diffusion models. The simulation results are in a good agreement with existing experimental data obtained from surface-wave sustained large-diameter plasmas. © 2002 The American Physical Society.

Low-pressure diffusion equilibrium of electronegative complex plasmas

A model for electronegative plasmas containing charged dust or colloidal grains was used. Numerical solutions based on the model demonstrate how a low-pressure diffusion equilibrium of the complex electronegative plasma system is dynamically sustained through plasma particle sources.

Effect of an internal rotating current on low-frequency inductively coupled plasmas

The effects of an inductively rotating current were observed on low-frequency inductively coupled plasmas. The spatial distribution of electromagnetic fields was investigated in a cylindrical metallic chamber filled with dense plasma. The distribution of the magnetic field in plasma chamber was observed for rarefied and dense plasmas. The plasma was assumed as uniform in the electromagnetic fields. The results showed the plasma density increased with power and the electron density increased with pressure.

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.

Two-dimensional simulation of nanoassembly precursor species in Ar+H2+C2H2 reactive plasmas

The results of two-dimensional fluid simulation of number densities and fluxes of the main building blocks and surface preparation species involved in nanoassembly of carbon-based nanopatterns in Ar+H2+C2H2 reactive plasmas are reported. It is shown that the process parameters and non-uniformity of surface fluxes of each particular species may affect the targeted nanopattern quality. The results can be used to improve predictability of plasma-aided nanofabrication processes and optimize the parameters of plasma nanotools.KGaA, Weinheim.