A.A. Howling

Frequency-Effects in Silane Plasmas for Plasma Enhanced Chemical Vapor-Deposition

It is now generally recognized that the excitation frequency is an important parameter in radio‐frequency (rf) plasma‐assisted deposition. Very‐high‐frequency (VHF) silane plasmas (50–100 MHz) have been shown to produce high quality amorphous silicon films up to 20 A/s [H. Curtins, N. Wyrsch, M. Favre, and A. V. Shah, Plasma Chem. Plasma Processing 7, 267 (1987)], and therefore the aim of this work is to compare the VHF range with the 13.56 MHz industrial frequency in the same reactor. The principal diagnostics used are electrical measurements and a charge coupled device camera for spatially resolved plasma‐induced emission with Abel inversion of the plasma image. We present a comparative study of key discharge parameters such as deposition rates, plasma uniformity, ion impact energy, power transfer efficiency, and powder formation for the rf range 13–70 MHz.

Time‐resolved measurements of highly polymerized negative ions in radio frequency silane plasma deposition experiments

The time-resolved fluxes of negative polysilicon hydride ions from a power-modulated rf silane plasma have been measured by quadrupole mass spectrometry and modeled using a simple polymerization scheme. Experiments were performed with plasma parameters suitable for high-quality amorphous silicon deposition. Polysilicon hydride anions diffuse from the plasma with low energy (approximately 0.5 eV) during the afterglow after the electron density has decayed and the sheath fields have collapsed. The mass dependence of the temporal behavior of the anion loss flux demonstrates that the plasma composition is influenced by the modulation frequency. The negative species attain much higher masses than the positive or neutral species and anions containing as many as sixteen silicon atoms have been observed, corresponding to the 500 amu limit of the mass spectrometer. This suggests that negative ions could be the precursors to particle formation. Ion-molecule and ion-ion reactions are discussed and a simple negative ion polymerization sheme is proposed which qualitatively reproduces the experimental results. The model shows that the densities of high mass negative ions in the plasma are strongly reduced by modulation frequencies near 1 kHz. Each plasma period is then too short for the polymerization chain to propagate to high masses before elementary anions are lost in each subsequent afterglow period. This explains why modulation of the rf power can reduce particle contamination. We conclude that for the case of silane rf plasmas, the initiation steps which ultimately lead to particle contamination proceed by negative ion polymerization.

Plasma silane concentration as a determining factor for the transition from amorphous to microcrystalline silicon in SiH4/H2 discharges

In this work, the microstructure transition from amorphous to microcrystalline silicon is defined in terms of the silane concentration in the plasma as opposed to the silane concentration in the input gas flow. In situ Fourier transform infrared absorption spectroscopy combined with ex situ Raman spectroscopy has been used to calibrate and validate this approach. Results show that a relevant parameter to obtain mu c-Si : H from SiH4/H-2 mixtures is the plasma composition, which is determined not only by the gas dilution ratio but also by the silane depletion fraction. It is also shown that mu c-Si : H can only be deposited efficiently, in terms of gas utilization, at a high rate by using high input concentration and depletion of silane.

Negative-Ion Mass-Spectra and Particulate Formation in Radio-Frequency Silane Plasma Deposition Experiments

Negative ions have been clearly identified in silane rf plasmas used for the deposition of amorphous silicon. Mass spectra were measured for monosilicon up to pentasilicon negative ion radical groups in power‐modulated plasmas by means of a mass spectrometer mounted just outside the glow region. Negative ions were only observed over a limited range of power modulation frequency which corresponds to particle‐free plasma conditions. The importance of negative ions regarding particulate formation is demonstrated and commented upon.

Improving plasma uniformity using lens-shaped electrodes in a large area very high frequency reactor

Experiments using a lens-shaped circular electrode are described to measure the correction of plasma nonuniformity due to the standing wave effect in a large area very high frequency plasma reactor. This work is the experimental verification of the theoretical reactor design in cylindrical geometry recently presented by L. Sansonnens and J. Schmitt, Appl. Phys. Lett. 82, 182 (2003). It is found that the lens-shaped electrode effectively compensates the standing wave effects by creating a uniform rf vertical electric field in the plasma volume. The plasma is uniform, except for edge effects, for a wide range of parameters and consequently the design is suitable for plasma processing.

Influences of a high excitation frequency (70 MHz) in the glow discharge technique on the process plasma and the properties of hydrogenated amorphous silicon

Hydrogenated amorphous silicon has been prepared at a plasma excitation frequency in the very‐high‐frequency band at 70 MHz with the glow discharge technique at substrate temperatures between 280 and 50 °C. The structural properties have been studied using hydrogen evolution, elastic recoil detection analysis, and infrared spectroscopy. The films were further characterized by dark and photoconductivity and by photothermal deflection spectroscopy. With respect to films prepared at the conventional frequency of 13.56 MHz considerable differences concerning the electronic and structural properties are observed as the substrate temperature is decreased from 280 to 50 °C. Down to a substrate temperature of 150 °C the electronic film properties change only a little and the total hydrogen content cH and the degree of microstructure that can be directly correlated to cH increase only moderately. Below 150 °C the electronic properties deteriorate in the usual manner but still the total hydrogen content does not ex...

A voltage uniformity study in large-area reactors for RF plasma deposition

Non-uniform voltage distribution across the electrode area results in inhomogeneous thin-film RF plasma deposition in large-area reactors. In this work, a two-dimensional analytic model for the calculation of the voltage distribution across the electrode area is presented. The results of this model are in good agreement with measurements performed without plasma at 13.56 MHz and 70 MHz in a large-area reactor. The principal voltage inhomogeneities are caused by logarithmic singularities in the vicinity of RF connections and not by standing waves. These singularities are only described by a two-dimensional model and cannot be intuitively predicted by analogy to a one-dimensional case. Plasma light emission measurements and thickness homogeneity studies of a-Si:H deposited films show that the plasma reproduces these voltage inhomogeneities. Improvement of the voltage uniformity is investigated by changing the number and position of the RF connections.

Particle agglomeration study in rf silane plasmas: In situ study by polarization-sensitive laser light scattering

To determine self-consistently the time evolution of particle size and their number density in situ multi-angle polarization-sensitive laser light scattering was used. Cross-polarization intensities (incident and scattered light intensities with opposite polarization) measured at 135 degrees and ex situ transmission electronic microscopy analysis demonstrate the existence of nonspherical agglomerates during the early phase of agglomeration. Later in the particle time development both techniques reveal spherical particles again. The presence of strong cross-polarization intensities is accompanied by low-frequency instabilities detected on the scattered light intensities and plasma emission. It is found that the particle radius and particle number density during the agglomeration phase can be well described by the Brownian free molecule coagulation model. Application of this neutral particle coagulation model is justified by calculation of the particle charge whereby it is shown that particles of a few tens of nanometer can be considered as neutral under our experimental conditions. The measured particle dispersion can be well described by a Brownian free molecule coagulation model including a log-normal particle size distribution

The physics of plasma-enhanced chemical vapour deposition for large-area coating: industrial application to flat panel displays and solar cells

Designing plasma-enhanced chemical vapour deposition (PECVD) reactors to coat large-area glass plates (similar to1 m(2)) for flat panel display or solar cell manufacturing raises challenging issues in physics and chemistry as well as mechanical, thermal, and electrical engineering, and material science. In such reactive glow discharge plasma slabs, excited at RF frequency (from 13.56 MHz up to similar to 100 MHz), the thin-film deposition uniformity is determined by the gas flow distribution, as well as the RF voltage distribution along the electrodes, and by local plasma perturbations at the reactor boundaries. All these aspects can be approached by analytical and numerical modelling. Moreover, the film properties are largely determined by the plasma chemistry involving the neutral radicals contributing to film growth, the effect of ion bombardment, and the formation and trapping of dust triggered by homogeneous nucleation. This paper will review progress in this field, with particular emphasis on modelling developments.

Anionic clusters in dusty hydrocarbon and silane plasmas

Measurements of anions and cations are reported for hydrocarbon and silane radio frequency capacitive glow discharges. Series of anions were observed by quadrupole mass spectrometry using power‐modulated plasmas, and their structures are interpreted from the form of the mass spectra. Various experiments in silane plasmas show that anion confinement results in particles and conversely, anion detrapping can inhibit particle formation. In contrast, the polymerized neutral flux magnitudes, mass spectra and dynamics are independent of the powder formation. Powder is known to form readily in deposition plasmas containing electronegative free radicals, and the general role of anions in particle formation is discussed in the light of these experiments.