Ch. Hollenstein

Surface modification of polyester films by RF plasma

Plasma treatment of PET films was carried out under argon, followed by exposure to an oxygen atmosphere. The films underwent considerable changes in surface composition and morphology, as demonstrated by contact angle measurements, FTIR-ATR, AFM, and XPS. It was found that the surface acquired oxygen containing polar functional groups such as -C=O, -OH, and -OOH, which increased in number as the plasma treatment time increased. During storage, the treated films underwent significant surface reorganization, and both the time and temperature contributed to the increase in the contact angle. As revealed by AFM measurements, these changes were accompanied by an increase in roughness in the form of ridges. The ridges were observed to grow in height with increasing treatment time, although their spacing showed little evolution. A correlation among the observations obtained from various techniques was established, giving a comprehensive picture of the structure and dynamics of plasma-treated PET surfaces

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.

Investigations of CH4, C2H2 and C2H4 dusty RF plasmas by means of FTIR absorption spectroscopy and mass spectrometry

Infrared (IR) absorption spectroscopy and mass spectrometry have been simultaneously applied to dusty radiofrequency (RF) plasmas in methane, acetylene and ethylene. The combination of IR absorption spectroscopy and mass spectrometry allows the chemical composition and structure of the most relevant plasma-produced neutral species, the ionic plasma composition and the chemical composition of the nanometer-sized particles to be precisely identified. The production of acetylenic compounds (C2Hx) seems to be a key mechanism for the powder formation in all the investigated hydrocarbon plasmas. Electron attachment to acetylenic compounds and the following ion-neutral reactions might lead to the high-mass carbon anions, which are trapped in the plasma and finally end in powder formation. The hydrogenation of the monomer strongly influences the composition of the ions. Finally the composition of the plasma-produced particles is mainly sp3 bonded carbon and the infrared spectra show similarities to that of polyethylene.

The physics and chemistry of dusty plasmas

An overview of the most recent experimental and modelling efforts on powder formation in reactive plasmas is given. The physics and chemistry of these dusty plasmas and their fundamental mechanisms leading to the production of nanometre-sized particles and their successive agglomeration leading to micrometre-sized particles are reviewed. The central role of particle charging and of charge fluctuations regarding the particle agglomeration is emphasised. Finally, the influence of the dust particles on the plasma parameters is described and an outlook on the most eminent problems towards the understanding of the reactive, dusty plasmas is given.

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.

Oxygen diluted hexamethyldisiloxane plasmas investigated by means of in situ infrared absorption spectroscopy and mass spectrometry

The gas phase species produced in rf plasmas of hexamethyldisiloxane (HMDSO), Si2O(CH3)6, diluted with oxygen, have been investigated. The complementarity of Fourier transform infrared absorption spectroscopy and mass spectrometry allows the determination of the most abundant neutral components present in the discharge. The measurements reveal that methyl groups (CH3), abundantly formed by the dissociation of the HMDSO molecule, are the precursor for the most abundant species which stem from two kinds of reaction. The first kind of reaction is combustion of CH3 by oxygen-producing formaldehyde (COH2), formic acid (CO2H2), carbon monoxide (CO), carbon dioxide (CO2) and water. It is shown that high mass carbonated radicals, such as SixOyCzHt, first diffuse to the surface and then the carbon is removed by oxygen etching to form CO2. The second is hydrocarbon chemistry promoted by CH3, producing mainly hydrogen (H2), methane (CH4) and acetylene (C2H2).

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.