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Influence of metallic atoms on nitrogen post-discharge
Bocková, Ivana ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The aim of this master thesis is to study the influence of metallic atoms on nitrogen post-discharge. Pure nitrogen post-discharge is a subject study of many works dealing with kinetic processes in plasma. Unfortunately, there are only a few published works that present influence of various traces on nitrogen post-discharge kinetics. This master thesis deals with problems of nitrogen post-discharge containing mercury traces. All experimental data were obtained using optical emission spectroscopy of a DC discharge in a flowing mode, which can achieve appropriate temporal resolution in the order of milliseconds. Spectra emitted during the post-discharge were recorded in the range of 320-780 nm and the following molecular spectral systems were identified: • 1. positive system of nitrogen: N2(B) -> N2(A), • 2. positive system of nitrogen: N2(C) -> N2(B), • 1. negative system of nitrogen: N2+(C) -> N2+(X), • NO-beta system: NO(B) -> NO(X). Besides them we were able to record the mercury line at 254 nm, only (in the spectrum of the first as well as in the second order); no other mercury lines were observed. The mercury vapor was introduced into the system at selected post-discharge time. Dependence of selected molecular band head intensities as well as mercury line intensity on experimental conditions (pressure, discharge power, wall temperature, time of mercury vapor introduction) were observed in time evaluation. The data obtained in pure nitrogen were used as a reference. The obtained results showed very high sensitivity of kinetic processes on mercury atoms presence. If mercury was introduced into the post-discharge the mercury line was observable around the site where mercury vapor was introduced into the discharge. The experimental data showed that mercury line intensity was directly proportional to the mercury atoms concentration and saturation effect could be observed. The energy level diagram demonstrates that the observed mercury line can be excited by collisions with nitrogen ground state molecule excited to vibrational level 18. Thus the mercury can be used for the monitoring of population at this vibrational level. Finally we obtained the population profile at this nitrogen metastable level during the post-discharge. The presented work demonstrates possibility of mercury atoms application for the monitoring of one nitrogen metastable state. Unfortunately, the contemporary data are not sufficient for the measurement of metastable absolute concentration. However, complex understanding of nitrogen post-discharge kinetics is still an open problem. Therefore a lot of future work should be done although the presented work brings a good fundament for such research.
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Optical emission spectoscopy of the nitrogen-argon post-discharge
Žáková, Marie ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The study of plasmas generated in pure nitrogen and their afterglows are a subject of many hundreds works bringing a lot of information about the kinetic processes and energy transfer reactions. The effect of nitrogen pink afterglow has a specific position among the other kinds of discharges and post-discharges. The post-discharge, and especially the pink afterglow, is extremely sensitive to the presence of various impurities and experimental conditions (total gas pressure in a discharge tube, temperature, etc.) because of their significant influence on all kinetic processes. That is the reason, why it is so important to study this processes. The DC flowing afterglow (generated using the hollow molybdenum electrodes in the distance of 12 cm, power ± 290 W) was used for the experimental part of this work. The discharge was created in Pyrex discharge tube at different concentration ratio of nitrogen and argon. The total gas presure was in range from 500 Pa to 5000 Pa. The emission spectra of post-discharge were recorded by TRIAX 550 spectrometer with CCD detector in the range of 320-780 nm. The vibrational populations at individual vibrational levels were calculated using the emission bands of the first (N2 (B 3g) N2 (A 3u+)) and the second (N2 (C 3u) N2 (B 3g)) positive and the first negative (N2+ (B 2u+) N2+ (X 2g+) nitrogen spectral systems. The dependencies of intensity on decay time and relative vibrational populations on argon concentration and pressure were obtained. The pink afterglow was very sharp in pure nitrogen at low pressure. With the increasing total pressure it was shifted to the later decay times and it was visible for longer time, too. The same effect was observed with the increase of argon concentration in the gas mixture. At the highest argon concentrations, especially at lower pressure, the effect of pink afterglow dissapeared. The knowledge of these processes can give the solution of all kinetic reactions in plasma and this can be used in plasma chemistry and for development of new technologies. This will be a subject of further intensive studies.
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Diagnostics of thin layer deposition using dimethylphenylsilane monomer
Procházka, Michal ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The aim of this thesis is a study of processes during organosilicone thin film deposition via plasma polymerization. Recently, thin films are the most expanding way of surface modification of materials. They are used as protective coatings, functional layers, they can increase or decrease adhesion to different compounds (e.g. water), or just improve mechanical properties of bulk materials. Plasma polymers, which are not known so long, are a modern trend in evolution of thin film deposition. They have perfect adhesion to the substrate and they are highly resistant against most of chemical compounds. Their structure is quite different from the structure of classical polymers. Recently, organosilicon compounds are used as precursors for plasma polymers because silicon built in the structure of plasma polymer allows thin film deposition on glass substrate and the organic part of monomer gives us infinite possibilities of modification. In our case dimethylphenylsilane (DMPS) was used as a monomer. Various RF low pressure discharges were used during this study. Plasma diagnostic was performed by optical emission spectroscopy of inductive coupled plasma. This method allows us to determine plasma composition during the deposition process. Thus we can predict the composition of deposited thin film according to input parameters. From relative populations of fragments we are able to find out optimal conditions for deposition process. We can also calculate temperature of particles in plasma which gives us some information about particle energies. The first part of the study deals with the identification of particles (fragments) created by fragmentation of monomer in plasma environment. We successfully identified hydrogen atomic lines of Balmer’s series in the spectra. Many rotational lines of hydrogen molecule were also detected. Atomic carbon occurred only in small amount. Much more carbon was detected in the form of CH radical. We also found some weak lines connected to atomic silicon. When we used a mixture of DMPS and oxygen, OH radical and O2+ were present in spectra. Next, optimal settings of deposition were determined for particular fragments from relative intensities of these fragments in optical emission spectra. Using this information we are able to set up the process to deposit thin films of desired composition and properties. We calculated electron temperature from intensities of hydrogen lines in Balmer’s series. Rotational temperature was obtained from CH radical intensity. Unfortunately, there was no convenient radical from which intensity we would be able to calculate vibrational temperature. All results and information obtained during the research can be used in industrial plasma polymerization processes and development of new coatings and functional thin films. Other studies on DMPS or similar monomer may also be realized to get more knowledge about processes in plasma and this thesis could serve as a basis for further research. Moreover, this study is a part of an international project. The aim of this project is to study processes during plasma polymerization both theoretically and practically. Once finished, the project and its results will be presented in scientific literature and at international conferences.
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Influence of metallic atoms on nitrogen post-discharge
Bocková, Ivana ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The aim of this master thesis is to study the influence of metallic atoms on nitrogen post-discharge. Pure nitrogen post-discharge is a subject study of many works dealing with kinetic processes in plasma. Unfortunately, there are only a few published works that present influence of various traces on nitrogen post-discharge kinetics. This master thesis deals with problems of nitrogen post-discharge containing mercury traces. All experimental data were obtained using optical emission spectroscopy of a DC discharge in a flowing mode, which can achieve appropriate temporal resolution in the order of milliseconds. Spectra emitted during the post-discharge were recorded in the range of 320-780 nm and the following molecular spectral systems were identified: • 1. positive system of nitrogen: N2(B) -> N2(A), • 2. positive system of nitrogen: N2(C) -> N2(B), • 1. negative system of nitrogen: N2+(C) -> N2+(X), • NO-beta system: NO(B) -> NO(X). Besides them we were able to record the mercury line at 254 nm, only (in the spectrum of the first as well as in the second order); no other mercury lines were observed. The mercury vapor was introduced into the system at selected post-discharge time. Dependence of selected molecular band head intensities as well as mercury line intensity on experimental conditions (pressure, discharge power, wall temperature, time of mercury vapor introduction) were observed in time evaluation. The data obtained in pure nitrogen were used as a reference. The obtained results showed very high sensitivity of kinetic processes on mercury atoms presence. If mercury was introduced into the post-discharge the mercury line was observable around the site where mercury vapor was introduced into the discharge. The experimental data showed that mercury line intensity was directly proportional to the mercury atoms concentration and saturation effect could be observed. The energy level diagram demonstrates that the observed mercury line can be excited by collisions with nitrogen ground state molecule excited to vibrational level 18. Thus the mercury can be used for the monitoring of population at this vibrational level. Finally we obtained the population profile at this nitrogen metastable level during the post-discharge. The presented work demonstrates possibility of mercury atoms application for the monitoring of one nitrogen metastable state. Unfortunately, the contemporary data are not sufficient for the measurement of metastable absolute concentration. However, complex understanding of nitrogen post-discharge kinetics is still an open problem. Therefore a lot of future work should be done although the presented work brings a good fundament for such research.
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Diagnostics of thin layer deposition using dimethylphenylsilane monomer
Procházka, Michal ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The aim of this thesis is a study of processes during organosilicone thin film deposition via plasma polymerization. Recently, thin films are the most expanding way of surface modification of materials. They are used as protective coatings, functional layers, they can increase or decrease adhesion to different compounds (e.g. water), or just improve mechanical properties of bulk materials. Plasma polymers, which are not known so long, are a modern trend in evolution of thin film deposition. They have perfect adhesion to the substrate and they are highly resistant against most of chemical compounds. Their structure is quite different from the structure of classical polymers. Recently, organosilicon compounds are used as precursors for plasma polymers because silicon built in the structure of plasma polymer allows thin film deposition on glass substrate and the organic part of monomer gives us infinite possibilities of modification. In our case dimethylphenylsilane (DMPS) was used as a monomer. Various RF low pressure discharges were used during this study. Plasma diagnostic was performed by optical emission spectroscopy of inductive coupled plasma. This method allows us to determine plasma composition during the deposition process. Thus we can predict the composition of deposited thin film according to input parameters. From relative populations of fragments we are able to find out optimal conditions for deposition process. We can also calculate temperature of particles in plasma which gives us some information about particle energies. The first part of the study deals with the identification of particles (fragments) created by fragmentation of monomer in plasma environment. We successfully identified hydrogen atomic lines of Balmer’s series in the spectra. Many rotational lines of hydrogen molecule were also detected. Atomic carbon occurred only in small amount. Much more carbon was detected in the form of CH radical. We also found some weak lines connected to atomic silicon. When we used a mixture of DMPS and oxygen, OH radical and O2+ were present in spectra. Next, optimal settings of deposition were determined for particular fragments from relative intensities of these fragments in optical emission spectra. Using this information we are able to set up the process to deposit thin films of desired composition and properties. We calculated electron temperature from intensities of hydrogen lines in Balmer’s series. Rotational temperature was obtained from CH radical intensity. Unfortunately, there was no convenient radical from which intensity we would be able to calculate vibrational temperature. All results and information obtained during the research can be used in industrial plasma polymerization processes and development of new coatings and functional thin films. Other studies on DMPS or similar monomer may also be realized to get more knowledge about processes in plasma and this thesis could serve as a basis for further research. Moreover, this study is a part of an international project. The aim of this project is to study processes during plasma polymerization both theoretically and practically. Once finished, the project and its results will be presented in scientific literature and at international conferences.
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Optical emission spectoscopy of the nitrogen-argon post-discharge
Žáková, Marie ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The study of plasmas generated in pure nitrogen and their afterglows are a subject of many hundreds works bringing a lot of information about the kinetic processes and energy transfer reactions. The effect of nitrogen pink afterglow has a specific position among the other kinds of discharges and post-discharges. The post-discharge, and especially the pink afterglow, is extremely sensitive to the presence of various impurities and experimental conditions (total gas pressure in a discharge tube, temperature, etc.) because of their significant influence on all kinetic processes. That is the reason, why it is so important to study this processes. The DC flowing afterglow (generated using the hollow molybdenum electrodes in the distance of 12 cm, power ± 290 W) was used for the experimental part of this work. The discharge was created in Pyrex discharge tube at different concentration ratio of nitrogen and argon. The total gas presure was in range from 500 Pa to 5000 Pa. The emission spectra of post-discharge were recorded by TRIAX 550 spectrometer with CCD detector in the range of 320-780 nm. The vibrational populations at individual vibrational levels were calculated using the emission bands of the first (N2 (B 3g) N2 (A 3u+)) and the second (N2 (C 3u) N2 (B 3g)) positive and the first negative (N2+ (B 2u+) N2+ (X 2g+) nitrogen spectral systems. The dependencies of intensity on decay time and relative vibrational populations on argon concentration and pressure were obtained. The pink afterglow was very sharp in pure nitrogen at low pressure. With the increasing total pressure it was shifted to the later decay times and it was visible for longer time, too. The same effect was observed with the increase of argon concentration in the gas mixture. At the highest argon concentrations, especially at lower pressure, the effect of pink afterglow dissapeared. The knowledge of these processes can give the solution of all kinetic reactions in plasma and this can be used in plasma chemistry and for development of new technologies. This will be a subject of further intensive studies.
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