On the Powder Formation in the Plasma Enhanced Chemical Vapor Deposition Process for the Deposition of SiOx Barrier Coatings

Nowadays thin films play an important role in everyday life and in industries. Thin film technology has been developed primarily for the growing demand for development of smaller and smaller devices that require advanced materials and new processing techniques suitable for micro and nano technology. One of the methods of producing thin films is by means of plasma technology. This is a technique by which plasma, also known as 'the fourth state of matter', is used to generate ions, electrons and radicals which deposit at a surface where they will form a thin film. The source of these depositing species could be either gaseous, liquid or solid in origin. Most of the time a plasma is generated by means of an electrical discharge. Plasma technologies are used for various applications. One of these is Plasma Enhanced Chemical Vapor Deposition (PECVD). PECVD systems have widespread applications in the electronic sector, because of their exibility in depositing different films such as silicon oxide thin films (SiOx). These films, currently deposited by organosilicon compounds, such as hexamethyldisiloxane (HMDSO), have dielectric and good barrier properties. The aim of the work at CRPP consists in optimizing PECVD processes for the deposition of these films on polymers. In this study, the species in gaseous phase and the powder produced in oxygen-diluted HMDSO plasmas were experimentally characterized in a radiofrequency (RF) capacitively-coupled reactor at 13.56 MHz. The gaseous phase of these plasmas and the particle formation were studied by in-situ infrared absorption spectroscopy and optical emission spectroscopy. The study of the powder formation is important because the particle deposition imposes an upper limit on the deposition rate. Particle formation was firstly studied as a function of HMDSO/O2 ratio. Analysis of the time evolution of the infrared absorption spectra gives the development of the size, the number density, the structure and the particle composition. At high oxygen dilution the formation of large particles is observed. The analysis of HMDSO/O2 plasma at low O2 content suggests that at the beginning of the process very small particles are formed by polymerization; the same particles do not grow much and keep sizes around 50 nm. The admixture of inert or non-reactant gases, such as Ar or N2, into the plasma promotes polymerization of the monomer; a high value of one of these inert or non-reactant gases leads to small powder particle size, since only polymerization takes place in this case. Particle size around 50 nm is also found in this case. At the same time we see a decrease of the carbon content and a weak reduction of the stoichiometry in SiOx indicated by the shift of the SiOSi asymmetric stretching vibration. This reduction also influences the deposited layers, less oxidized and, thus, quite far from a stoichiometric character. Hexamethyldisilazane (HMDSN) and tetramethylsilane (TMS) are other reagents that have been identified as alternatives to HMDSO. The in-situ infrared absorption spectra show that HMDSO/O2 and HMDSN/O2 plasmas are quite similar, but in the second case a lower SiOSi stretching peak intensity, due to NH and SiN peaks, is seen. TMS/O2 and HMDSN/O2 plasma spectra show a low SiOSi bending and stretching peak intensity, due also to the oxygen atom absence in their chemical structure. Two separate chapters are respectively devoted to the silicon nitride thin films (SiNx) and plasma crystal formation. SiNx layers are deposited by three different organosilicon compounds, such as HMDSN, TMS and bis(dimethylamino)dimethylsilane (BDMADMS). No powder formation is visualized in this contest. The ex-situ infrared absorption spectra show the difficulty to produce stable SiNx films; they present a low SiN peak intensity and are quite hygroscopic. Furthermore, in HMDSO/O2 plasmas at high oxygen dilution and high pressure, later in time into the discharge, accretion leads to larger and larger particles which can finish up in particles forming a plasma crystal. The study of RF harmonics shows the presence of instabilities, clear indications of the passage from small particulate to plasma crystal structure.

Etude de l'origine et de la croissance de particules submicrométriques dans les plasmas radiofréquence réactifs

Christian Deschenaux

The formation of sub-micron sized particulates has been studied in a low pressure (0.1 mbar) radio-frequency (13.56 MHz) capacitively coupled plasma discharge. Particles are studied in situ by infrared absorption spectroscopy, laser illumination and Cavity Ring Down Absorption Spectroscopy. Transmission Electron Microscopy was applied ex situ for particulates collected during the plasma. We propose that two principal mechanisms may be involved in the formation of these particulates: formation and trapping of negative ions in the gaseous phase, and the recycling of material deposited on the electrodes during the discharge, by film erosion or delamination. The relative importance of these two mechanisms was studied in silane, methane, ethylene and acetylene plasmas. The growth of the particulates in silane plasmas, monitored with Infrared and Cavity Ring Down Absorption Spectroscopy, allowed us to distinguish an increasing volume growth phase followed by an agglomeration phase at constant volume, in agreement with the literature. A slight powder and film recycling effect is detected as the experiments are repeated, as observed by an increasing particle size. The hydrogen content of powder formed in silane plasmas was estimated in situ by infrared absorption spectroscopy and changes in the infrared absorption spectrum could be observed for silane diluted with hydrogen and argon. In particular, the porous structure of the powder was observed from the high content of surface related vibration bonds relative to bulk related bonds. Photoluminescence was detected for the particles at 2.15eV that could possibly be attributed to the crystalline structure of the particles. Infrared Absorption Spectroscopy and mass spectrometry applied in situ showed that acetylenic compounds are preferentially produced in methane, ethylene and acetylene plasmas and that the hydrogen content of the other species produced in these plasmas depends on the initial gas hydrogen content. Negative ions were evidenced in these plasmas and a polymerization reaction is proposed between acetylene and C2nHx- negative ions to explain the formation of particle's precursors. The formation of aromatic structures is suggested for n>3. The different relative abundance of C2Hx- ions is proposed to explain the different powder production rates with different initial gases or different fluxes. Hydrogen may inhibit the formation of high-mass negative ions and particles. Fast growth of spherical amorphous carbon particles (∼100s) was observed for a low pressure (0.1 mbar) acetylene plasma. The sp3 structure was confirmed in situ by infrared absorption spectroscopy. Slow growth (∼1000s) of irregularly shaped particles is observed for methane plasmas at the same pressure and power. Particle heterogeneity was studied with Transmission Electron Microscopy and showed graphitic onions, multiwalled nanotubes, flakes and agglomerates attributed to the erosion or the delamination of the deposited carbon layer. The influence of the recycling of the deposited layer on the powder formation was observed in situ from enhanced particle formation as the experiments were repeated. A similar behavior was observed for discharges containing mixtures of hexamethyldisiloxane, oxygen and helium. Keeping in mind that the control of powder homogeneity implies a control over the reactor contamination and its history, we conclude that an important part of the particulates formed in the discharges studied depends on the gas phase reactions, determined by the plasma chemistry.

EPFL2002

Process monitoring of alumina nanoparticle synthesis by inductively coupled RF thermal plasma

Jong-Won Shin

Since the first inductively coupled plasma (ICP) torch was developed in the 60's, RF thermal plasmas have found a variety of applications in material processing such as crystal growth, thermal spray coatings, spheroidization and vaporization of refractory materials. In recent decades, inductively coupled thermal plasmas have been used for the synthesis of high purity nanoparticles, thank to their remarkable advantages such as high energy density, variable operating pressures and low product contamination. The formation of nano-sized particles in thermal plasmas particularly using solid refractory precursor is a complex process. Hereby the injected precursor powders are heated by the high temperature of the thermal plasma. The heated powders are vaporized and decomposed into vapor species. During the following cooling, the vapor species are condensed to nano-sized particles. In this synthesis process, characterized by evaporation-condensation, the properties of the synthesized particles such as particle size, size distribution, phases and morphology are affected by various process parameters. Gas pressure, flow rates of the different torch gases, size of the precursor powders and powder loading in the plasma are considered as the influencing process parameters. In order to optimize and control the process for tailor-made nanoparticle synthesis, it is necessary to understand the effects of the process parameters on plasma properties and on the particle-plasma interactions resulting in final properties of the synthesized powders. In the present work, firstly, the enthalpy probe technique, a well-established plasma diagnostic tool for high pressure thermal plasma, has been applied to characterize the inductively coupled Ar-H2 thermal RF plasma used for alumina nanoparticle synthesis at different operating conditions. The plasma enthalpy has been determined, and the plasma temperature under a given gas pressure could subsequently be calculated assuming local thermodynamic equilibrium (LTE), once the gas composition has been determined by mass spectrometry. The gas velocity of the plasma jet could also be obtained by using the Bernoulli equation and stagnation pressure. Secondly, the influence of flow rates of central gas and precursor feed rates on the Al2O3 precursor evaporation has been investigated by process monitoring. Optical emission spectroscopy (OES) and laser light extinction (LE) measurements have been carried out to monitor in-situ the injection of the alumina precursors and to obtain information on the ongoing precursor evaporation. The emission line intensities of the aluminum vapor were used to determine the dependence of process parameters on precursor evaporation. Furthermore, the laser light extinction was used to calculate the number density of non plasma-treated powders, from which the number fraction of evaporated powders could be deduced. The size and morphology of the synthesized particles have been characterized ex-situ. Finally, the influence of quenching conditions on the condensation and formation of the nano-sized alumina particle has been studied by process analysis of the gas phase reactions of alumina. Optical emission spectroscopic was performed at different axial positions to monitor the gas phase reactions of the vaporized particles. Axial profiles of the emission line intensities of the main vapor species of alumina, Al(g) and AlO(g), were compared with the results of the enthalpy probe measurements and the thermal decomposition reactions of alumina found in literature. The results allow explanation of the alumina reactions in the thermal plasma as well as gives indications for the optimal axial position of the quenching gas injection. In addition to the determination of the optimal quenching position, the influence of the flow rates of quenching gas on the nanoparticle formation has been investigated. The synthesis of the submicron alumina using vapor-condensation principle predominantly leads to various thermodynamically metastable crystal structures called transition alumina. Therefore, the occurrence of different transition aluminas is discussed with regards to the flow rates of the quenching gas. The results presented in this thesis show that the synthesis process of the nanoparticle can be described on the basis of experimental results and basic information on the powder materials. The explanation of the influence of process parameters on powder evaporation and nanoparticle formation shows the usefulness of the in-situ plasma process monitoring, and the large potential for optimizing and controlling the nanopowder synthesis process in an inductively coupled RF thermal plasma.

EPFL2006

Design, characterisation and modelling of a high current DC arc plasma source for silicon and silicon carbide processing at low pressure

Lukas Derendinger

In the frame of this thesis, two similar high current DC arc (HCDCA) plasma sources were investigated in a low gas pressure regime (10-3-10-2 mbar). One of them was initially designed for the epitaxial growth of silicon and silicon germanium (LEP), the other for the industrial deposition of diamond (BAI). The LEP source was analysed using pure argon plasmas. Measurements of the ion saturation current were performed with a custom-built multi-Langmuir probe to analyse plasma density homogeneity. Plasma instabilities at 50 Hz were observed and studied by different means. One source of the instability is the AC current used for the filament heating, whereas lower frequency instabilities are due to the use of a ring shaped anode. A sensitive Hall sensor was used to measure the magnetic field induced by the discharge current. It was found that depending on the plasma parameters gas pressure and external magnetic field the current tends to attach at different points on the anode, leading to a complete loss of reactor symmetry. The installation of an additional cusp field around the reactor chamber lead to an increase of the overall homogeneity of the plasma density, but it could not resolve the problems of current attachment. In the following the ring anode was replaced by a point anode and the maximum external magnetic field strength was increased by a factor of ten. With a novel multi-Hall probe the current density of the now columnar shaped plasma was measured, showing a strongly peaked current density profile, when an external magnetic field is applied. Together with ion saturation current measurements made with a Langmuir probe, the electron temperature inside the plasma column was estimated to be about 4 eV. In earlier works made on the BAI reactor the high dissociation efficiency of the HCDCA plasma source has already been shown. Optical emission spectra were compared between RF plasmas, low pressure (1.5mbar) HCDCA plasmas and our very low pressure (10-3-10-2 mbar) HCDCA plasmas. The dominating species found in RF plasma spectra are molecular, the spectra of low pressure HCDCA plasmas are dominated by atomic species and the spectra of very low pressure HCDCA plasmas are dominated by ions, emphasising the high dissociation efficiency of this system. Silane and Methane was used as precursor gases in the BAI reactor for the deposition of silicon carbide films. Promising high deposition rates up to 9 nm/s were found, but FTIR spectroscopy showed high hydrogen and oxygen concentrations in the porous films, making the not optimised deposited material useless for the application of wear-resistant coatings. Microcrystalline hydrogenated silicon (µc-Si:H) is viewed as a cost- and energy-effective alternative to crystalline silicon for the production of solar cells. A detailed analysis of the deposition rate and the Raman crystallinity of µc-Si:H films deposited in the BAI reactor showed deposition rates up to 6.5 nm/s and a wide range of crystallinity from 0-80%. Film thickness inhomogeneity in silicon solar cells has to be less than 5%. To meet this standard a first substantial improvement was achieved with the installation of a linear gas injection along the plasma column. Tests on large surface glasses (47 × 37 cm2) revealed strong diffusive effects, which could be reproduced with a simple gas diffusion model. The model showed the necessity to reduce the dead volume around the plasma and to set the substrates as close as possible to the plasma column in order to minimise film thickness inhomogeneity due to diffusion. Deposition rate measurements made in these conditions assured the results of the model. The development of a method to estimate the dissociation efficiency of the plasma by simple pressure measurements showed also an important increase of the silane dissociation from 75-92% when the plasma is confined in a smaller volume. Therefore, compared to the reactor with a large dead volume, only a third of the initial silane is lost to the pumps.

EPFL2008