Title: Study of Glow Discharge in Oxygen and its Mixtures at Medium Pressures Author: Lukáš Schmiedt Department: Department of Surface and Plasma Science Supervisor: Doc. RNDr. Věra Hrachová, CSc. Department of Surface and Plasma Science Abstract: The positive column of DC glow discharge sustained in oxygen and oxygen-argon mixtures has been studied in two discharge tubes of the same shape made from different materials (Silica and Pyrex glass) for total pressures 200 - 1750 Pa and discharge currents up to 40 mA. Parameters of the discharge - electric field strength and emission spectra - were studied with respect to existence of the low- and high-gradient forms of the positive column of the discharge. We have focused on the qualitative analysis of the differences in emission spectra for both particular forms, as well as on possibility of determination of the rotational temperature of oxygen molecule under various discharge conditions, particularly with respect to the relative amount of the admixture. Keywords: glow discharge; oxygen; medium pressures; emission spectra

Avanços recentes no processo de Metalurgia do Pó possibilitaram a produção de ligas de alumínio com ótimas propriedades e capazes de serem aplicadas nas indústrias automotiva e aeroespacial. Dentre as principais vantagens destas ligas, estão, a baixa relação peso/resistência, a alta condutividade térmica e elétrica, e a alta resistência à corrosão sob vários ambientes. Este trabalho teve como objetivo o estudo de um processo alternativo de sinterização do alumínio baseado na aplicação de plasma produzido por descarga incandescente anômala. Pó de alumínio comercial foram misturadas com 1% em peso de estearato de zinco (como lubrificante) e então compactadas sob pressão de 600 Mpa. A dimensões das amostras compactadas (verdes) ficaram em aproximadamente 13mm de altura e 10mm de diâmetro e massa controlada em torno de 3,5g. A fim de analisar as diferenças das amostras antes e após o processo de sinterização, foram calculadas as densificações para cada corpo de prova produzido. Posteriormente, as amostras verdes compactadas passaram pelo processo de sinterização a plasma e convencional, ambas com temperatura (500ºC) e atmosfera definidas. A sinterização convencional foi realizada utilizando duas atmosferas, argônio puro e nitrogênio puro, e o processo a plasma empregou, além de argônio e nitrogênio, o gás hidrogênio. Após a sinterização as amostras foram caracterizadas quanto a densificação, dureza, composição química e rugosidade superficial, além disso, uma análise metalográfica foi realizada por Microscopia Eletrônica de Varredura (com EDS). Embora todas as atmosferas foram efetivas na sinterização a plasma, o nitrogênio foi capaz de produzir a menor redução de densificação nas amostras, bem como a maior dureza e a menor rugosidade, dentre as amostras tratadas a plasma. A utilização do plasma também gerou uma melhor extração do lubrificante, porém com um aumento significativo da rugosidade com relação ao processo convencional devido à ação do sputtering gerado pelo bombardeamento iônico. / The recent advances in Powder Metallurgy make possible the production of Aluminum alloys with great properties and applicable in the automotive and aerospace industries. Among the main advantages of these alloys, the low weight to strength rate, high thermal and electrical conductivity, and the high corrosion resistance under several environments can be pointed out. This work had as aim the investigation of an alternative sintering process for Aluminum based on plasma glow discharge. Aluminum commercial powder was mixed with 1 weight-% of Zinc Stearate (as lubricant) and then compacted under 600 MPa pressure. The dimension of the as compacted (green) samples were about 13mm of height and 10mm of diameter and the mass around 3.5g. In order to analyze the differences of samples before and after e sintering process, the densification was calculated for each sample individually. After that, the green samples were sintered by plasma and in a conventional resistive furnace with protected atmosphere, using predefined temperature (500ºC) and gas atmospheres. The conventional sintering was carried out using two different atmospheres pure Argon and pure Nitrogen, and in the plasma sintering, besides Argon and Nitrogen, Hydrogen was used. After sintering the samples were investigated for densification, hardness, chemical composition and roughness, besides that metallography analysis by Electronic Microscopy with EDS were performed. Although all atmospheres were effective in the plasma sintering, the Nitrogen was able to produce the lowest reduction in density, the highest hardness and the lowest roughness, among all tested plasma conditions. The use of plasma also was responsible for an more efficient extraction of the lubricant, however with a significant increase of the roughness in relation to the conventional process, which was attributed to the sputtering effect by ion bombardment.

Avanços recentes no processo de Metalurgia do Pó possibilitaram a produção de ligas de alumínio com ótimas propriedades e capazes de serem aplicadas nas indústrias automotiva e aeroespacial. Dentre as principais vantagens destas ligas, estão, a baixa relação peso/resistência, a alta condutividade térmica e elétrica, e a alta resistência à corrosão sob vários ambientes. Este trabalho teve como objetivo o estudo de um processo alternativo de sinterização do alumínio baseado na aplicação de plasma produzido por descarga incandescente anômala. Pó de alumínio comercial foram misturadas com 1% em peso de estearato de zinco (como lubrificante) e então compactadas sob pressão de 600 Mpa. A dimensões das amostras compactadas (verdes) ficaram em aproximadamente 13mm de altura e 10mm de diâmetro e massa controlada em torno de 3,5g. A fim de analisar as diferenças das amostras antes e após o processo de sinterização, foram calculadas as densificações para cada corpo de prova produzido. Posteriormente, as amostras verdes compactadas passaram pelo processo de sinterização a plasma e convencional, ambas com temperatura (500ºC) e atmosfera definidas. A sinterização convencional foi realizada utilizando duas atmosferas, argônio puro e nitrogênio puro, e o processo a plasma empregou, além de argônio e nitrogênio, o gás hidrogênio. Após a sinterização as amostras foram caracterizadas quanto a densificação, dureza, composição química e rugosidade superficial, além disso, uma análise metalográfica foi realizada por Microscopia Eletrônica de Varredura (com EDS). Embora todas as atmosferas foram efetivas na sinterização a plasma, o nitrogênio foi capaz de produzir a menor redução de densificação nas amostras, bem como a maior dureza e a menor rugosidade, dentre as amostras tratadas a plasma. A utilização do plasma também gerou uma melhor extração do lubrificante, porém com um aumento significativo da rugosidade com relação ao processo convencional devido à ação do sputtering gerado pelo bombardeamento iônico. / The recent advances in Powder Metallurgy make possible the production of Aluminum alloys with great properties and applicable in the automotive and aerospace industries. Among the main advantages of these alloys, the low weight to strength rate, high thermal and electrical conductivity, and the high corrosion resistance under several environments can be pointed out. This work had as aim the investigation of an alternative sintering process for Aluminum based on plasma glow discharge. Aluminum commercial powder was mixed with 1 weight-% of Zinc Stearate (as lubricant) and then compacted under 600 MPa pressure. The dimension of the as compacted (green) samples were about 13mm of height and 10mm of diameter and the mass around 3.5g. In order to analyze the differences of samples before and after e sintering process, the densification was calculated for each sample individually. After that, the green samples were sintered by plasma and in a conventional resistive furnace with protected atmosphere, using predefined temperature (500ºC) and gas atmospheres. The conventional sintering was carried out using two different atmospheres pure Argon and pure Nitrogen, and in the plasma sintering, besides Argon and Nitrogen, Hydrogen was used. After sintering the samples were investigated for densification, hardness, chemical composition and roughness, besides that metallography analysis by Electronic Microscopy with EDS were performed. Although all atmospheres were effective in the plasma sintering, the Nitrogen was able to produce the lowest reduction in density, the highest hardness and the lowest roughness, among all tested plasma conditions. The use of plasma also was responsible for an more efficient extraction of the lubricant, however with a significant increase of the roughness in relation to the conventional process, which was attributed to the sputtering effect by ion bombardment.

Cette thèse est consacrée à l'étude du conditionnement des parois des réacteurs de fusion, en particulier ITER. Le conditionnement est nécessaire pour contrôler l'état de surface de l'enceinte à vide et donc les performances des plasmas d'ITER.Le conditionnement du tokamak JET, ayant une paroi représentative de celle d'ITER, et son impact sur l'opération est étudié de manière approfondie.Un modèle 2D des décharges luminescentes de conditionnement est validé par des données expérimentales. Il prédit des décharges raisonnablement uniformes dans ITER.Des expériences de conditionnement sur JET montrent que l'échange isotopique est un moyen efficace pour contrôler l'inventaire de tritium dans ITER, l'efficacité d'élimination étant potentiellement comparable à la rétention prédite dans un plasma nominal.Un modèle 1D de l'hydrogène échange isotopique en béryllium est élaboré et validé. Il montre que la fluence et la température de surface déterminent l'efficacité de l'échange isotopique. / Thesis is devoted to studies of performance and efficiency of wall conditioning techniques in fusion reactors, such as ITER. Conditioning is necessary to control the state of the surface of plasma facing components to ensure plasma initiation and performance. Conditioning and operation of the JET tokamak with ITER-relevant material mix is extensively studied. A 2D model of glow conditioning discharges is developed and validated; it predicts reasonably uniform discharges in ITER. In the nuclear phase of ITER operation conditioning will be needed to control tritium inventory. It is shown here that isotopic exchange is an efficient mean to eliminate tritium from the walls by replacing it with deuterium. Extrapolations for tritium removal are comparable with expected retention per a nominal plasma pulse in ITER.A 1D model of hydrogen isotopic exchange in beryllium is developed and validated. It shows that fluence and temperature of the surface influence efficiency of the isotopic exchange.

In the present work, the abnormal glow discharge at atmospheric pressure was generated in the nitrogen-methane (1 to 5 %) gaseous mixtures related to the atmosphere of Titan. The discharge itself was monitored by optical emission spectrometry that confirmed presence of active nitrogen species and various radicals formed from methane. Besides them, the CN spectral bands were observed. Intensities of all light emitting species were studied in the dependence on applied power and composition of nitrogen-methane mixture. The rotational temperature of about 2000 K was calculated from the second positive nitrogen system. The vibrational temperature also obtained from neutral nitrogen molecule increased nearly directly with methane from 3000 K (1 % CH4) to 3600 K (5 % CH4). In the contrary, vibrational temperature obtained from nitrogen molecular ion decreased with methane in the gaseous mixture and increased with applied discharge power from 3700 K to 4200 K. The same trend showed the vibrational temperature calculated from violet system of CN with value from 4600 K to 5800 K. The stable discharge products were analysed by proton transfer time of flight mass spectrometry of the exhausting gas. Presence of many aliphatic and some aromatic hydrocarbons was confirmed as well as quite a lot of amino and cyano compounds. Increasing concentrations of methane have produced more substances with higher molecular weight and less simple substances that were likely to be consumed on more complex substances. Their relative intensities were determined under the same conditions as optical emission spectra were collected.

Glow Discharge Optical Emission Spectrometry (GD OES) has proved to be a versatile analytical technique for the direct analysis of solid samples. The application of a pulsed power supply to the glow discharge (GD) has a number of advantages in comparison with a continuous one and thereby broadens the analytical potential of the GD. However, because the pulsed GD (PGD) is a relatively new operation mode, the pulsing and plasma parameters as well as their influence on the analytical performance of the GD are not yet comprehensively studied. The aim of this dissertation consists in the investigation of the PGD features, which are crucial for both understanding the discharge plasma processes and analytical applications. The influence of the pulsing parameters on the PGD is ascertained and compared for direct current (dc) and radio frequency (rf) discharges. In the research attention is firstly paid on the electrical parameters of PGD, then on the sputtered crater shapes, sputtering rates and finally on the light emission. It is found that the sputtered crater shape is strongly affected by the duration of the applied pulses even when the duty cycle is fixed. The pulse length influences the intensity of the light emission as well (at constant duty cycle). Moreover this influence is different for emission lines of atoms and ions in the plasma. This phenomenon can be seen at the comparison of atomic and ionic lines of different elements. The voltage–current plots of the PGD are found to indicate heating of the discharge gas when operating at high duty cycles. Using this feature a new method for the estimation of the discharge gas temperature from the voltage-current characteristics of the PGD is developed. The calculated temperature values are compared with another temperature measurement technique. Different temperature estimation procedures have shown that the discharge gas temperature can be reduced by around 100 K when PGD is applied. The temperature measurements have also confirmed that the gas heating can be adjusted by variation of the pulsing parameters. The effect of sputtering on the Cu(In,Ga)Se2 (CIGSe) layer surface of the solar cells is described for the first time. SEM investigations of the CIGSe layer of the solar cells have shown that sputter induced effects can be reduced by variation of the pulsing parameters. With regard to the question whether dc and rf pulsed discharges behave similarly: nearly all phenomena found with dc discharges also appear in the rf case. Hence it is concluded that the pulsed rf and dc discharges are very similar in terms of the electrical properties, sputtered crater formation, light emission and temperature. It is concluded that matrix specific, as well as matrix independent quantification principles and the intensity correction developed by Arne Bengtson can be applied for the pulsed mode, if special conditions are fulfilled. CIGSe solar cell samples and thin layered electrode metallizations of SAW devices are measured and quantified with application of PGD. The proposed quantification procedures are performed at commercial GD OES devices and can be used for the analysis with application of pulsed rf discharge. The studies of the PGD performed in this dissertation are relevant for the application of the GD OES analysis in materials science. During the collaborative work with Helmholtz-Zentrum Berlin für Materialien und Energie and with the research group of Dr. Thomas Gemming at IFW Dresden the optimized pulsed GD OES measurements could be successfully applied at the investigation of thin film solar cells with CIGSe light absorbing layer and electrode matallizations of SAW devices. In case of solar cell samples pulsed GD OES depth profiling along with SIMS measurements reveal the role of the Al2O3 barrier layer in high efficiency solar cells consisting of a CIGSe/Mo/Al2O3/steel substrate layer stack (the barrier layer is to prevent the Fe diffusion into the CIGSe). The features of the CIGSe films growth are studied with help of pulsed GD OES and in situ synchrotron XRD measurements. The diffusion coefficient of Zn into the CuInS2 layer is determined for the first time from the measured GD OES depth profiles of the corresponding solar cell samples. In case of SAW samples, pulsed GD OES measurements helped to evaluate the different SAW electrode preparation procedures and to select the most suitable one. In addition pulsed GD OES depth profiling along with XPS, TEM-EDX and electrode lifetime measurements indicate the possible mechanism of power durability and lifetime improvement of the SAW devices when a small amount of Al is added to the Cu-based electrodes. / Die optische Glimmentladungsspektroskopie (engl. Glow Discharge Optical Emission Spectrometry - GD OES) hat sich als eine vielfältige und schnelle Methode für die direkte Analyse von festen Materialien erwiesen. Die Anwendung von gepulsten Glimmentladungen (GD) bietet eine Reihe von Vorteilen im Vergleich zu einer kontinuierlichen Entladung und erweitert dadurch das analytische Potential der Methode. Die praktische Anwendung von gepulsten GD erfordert jedoch ein tiefes Verständnis der Prozesse, die in der Entladung und im elektrischen System ablaufen. Der Einfluss der Puls- und Plasmaparameter auf die analytische Leistung der gepulsten GD ist bislang noch nicht umfassend erforscht worden. Die Zielstellung dieser Arbeit besteht in der Untersuchung der Eigenschaften der gepulsten GD, welche von besonderer Bedeutung sowohl für das Verständnis des Entladungsprozesses als auch für analytische Anwendungen ist. Die Auswirkungen der Pulsparameter auf die gepulste GD wurde für den Gleichstrom-(DC) und Hochfrequenz- (HF) Modus untersucht und verglichen. Die Reihenfolge der Untersuchungen wurde in dieser Arbeit wie folgt gewählt: elektrische Parameter, Sputterkraterformen, Sputterraten und Lichtemission. Die Form des Sputterkraters korreliert stark mit der Pulsdauer, selbst wenn das Tastverhältnis konstant ist. Die Pulsdauer beeinflusst nicht nur die Kraterform, sondern auch die Intensität der Emissionslinien (bei konstantem Tastverhältnis). Darüber hinaus ist dieser Einfluss unterschiedlich für Atome und Ionen. Dieses Verhalten wurde an mehreren Emissionslinien (atomar bzw. ionisch) nachgewiesen. Aus der Analyse der U-I-Kennlinien der gepulsten GD ergab sich, dass es zu einer Erhitzung des Plasmas bei höherem Tastverhältnis kommt. Dieser Effekt wurde zur Bestimmung der Plasma-Gastemperatur ausgenutzt. Die ermittelten Temperaturen wurden mit einer andere Methode verglichen. Aus der Abschätzung ergab sich, dass die Plasmatemperatur bei gepulsten GD um bis zu 100 K gesenkt werden und durch die Pulsparameter genauer eingestellt werden kann. Der Einfluss des Sputterns auf Cu(In,Ga)Se2 (CIGSe) Dünnschichten von Solarzellen wurde erstmals beschrieben. REM-Untersuchungen an GD-gesputterten CIGSe Schichten haben gezeigt, dass die Sputtereffekte durch die Variation der Pulsparameter reduziert werden können. Es konnte gezeigt werden, dass HF- und DC-Entladungen dieselben Effekte aufweisen und sich nur geringfügig voneinander unterscheiden. Daraus kann geschlussfolgert werden, dass DC- und HF-Entladungen in Bezug auf elektrische Eigenschaften, Kraterformen, Lichtemission und Temperatur sehr ähnlich sind. Die Quantifizierung der mit gepulsten GD gemessenen Tiefenprofile ergab ferner, dass die Anwendung der Quantifizierungsmethoden für den kontinuierlichen Modus unter den gegebenen Bedingungen zulässig ist. Die Tiefenprofile von Solarzellen-Schichten sowie SAW-Metallisierungen wurden anhand gepulster GD gemessen und quantifiziert. Die empfohlenen Quantifizierungsmethoden können mit kommerziellen GD OES-Geräten durchgeführt werden. Die Untersuchungen an gepulsten GD sind insbesondere relevant für GD OES-Anwendungen im Bereich der Werkstoffwissenschaft. Während der Zusammenarbeit mit dem Helmholtz-Zentrum Berlin für Materialien und Energie und der Arbeitsgruppe von Dr. Thomas Gemming (IFW Dresden) konnten optimierte, gepulste GD OES Messungen erfolgreich zur Untersuchung von Dünnschicht-Solarzellen bzw. hochleistungsbeständigen SAW-Metallisierungen angewendet werden. Für die Solarzellen haben GD OES und SIMS Messungen geholfen, die Rolle der Al2O3-Barriere in CIGSe/Mo/Al2O3 Schichtstapeln auf flexiblem Stahlsubstrat besser zu verstehen (Al2O3 soll die Diffusion der Fe-Atome in CIGSe verhindern). Die gemeinsame Untersuchung getemperter CIGSe-Schichten mit gepulster GD OES und in-situ Synchrotron-XRD ergab neue Erkenntnisse zum Schichtwachstum. Der Diffusionskoeffizient von Zn in CuInS2 wurde erstmals aus GD OES-Tiefenprofilen bestimmt. Im Fall der SAW-Metallisierungen konnte die GD OES zur Bestimmung des geeignetsten Herstellungsverfahrens einen wichtigen Beitrag leisten. Die gepulste GD OES hat neben anderen Untersuchungsmethoden wie TEM-EDX, XPS und Lebensdauermessungen die Verbesserung der Leistungsbeständigkeit von Cu-Metallisierungen durch geringen Al-Zusatz aufklären können.

Glow Discharge Optical Emission Spectrometry (GD OES) has proved to be a versatile analytical technique for the direct analysis of solid samples. The application of a pulsed power supply to the glow discharge (GD) has a number of advantages in comparison with a continuous one and thereby broadens the analytical potential of the GD. However, because the pulsed GD (PGD) is a relatively new operation mode, the pulsing and plasma parameters as well as their influence on the analytical performance of the GD are not yet comprehensively studied. The aim of this dissertation consists in the investigation of the PGD features, which are crucial for both understanding the discharge plasma processes and analytical applications. The influence of the pulsing parameters on the PGD is ascertained and compared for direct current (dc) and radio frequency (rf) discharges. In the research attention is firstly paid on the electrical parameters of PGD, then on the sputtered crater shapes, sputtering rates and finally on the light emission. It is found that the sputtered crater shape is strongly affected by the duration of the applied pulses even when the duty cycle is fixed. The pulse length influences the intensity of the light emission as well (at constant duty cycle). Moreover this influence is different for emission lines of atoms and ions in the plasma. This phenomenon can be seen at the comparison of atomic and ionic lines of different elements. The voltage–current plots of the PGD are found to indicate heating of the discharge gas when operating at high duty cycles. Using this feature a new method for the estimation of the discharge gas temperature from the voltage-current characteristics of the PGD is developed. The calculated temperature values are compared with another temperature measurement technique. Different temperature estimation procedures have shown that the discharge gas temperature can be reduced by around 100 K when PGD is applied. The temperature measurements have also confirmed that the gas heating can be adjusted by variation of the pulsing parameters. The effect of sputtering on the Cu(In,Ga)Se2 (CIGSe) layer surface of the solar cells is described for the first time. SEM investigations of the CIGSe layer of the solar cells have shown that sputter induced effects can be reduced by variation of the pulsing parameters. With regard to the question whether dc and rf pulsed discharges behave similarly: nearly all phenomena found with dc discharges also appear in the rf case. Hence it is concluded that the pulsed rf and dc discharges are very similar in terms of the electrical properties, sputtered crater formation, light emission and temperature. It is concluded that matrix specific, as well as matrix independent quantification principles and the intensity correction developed by Arne Bengtson can be applied for the pulsed mode, if special conditions are fulfilled. CIGSe solar cell samples and thin layered electrode metallizations of SAW devices are measured and quantified with application of PGD. The proposed quantification procedures are performed at commercial GD OES devices and can be used for the analysis with application of pulsed rf discharge. The studies of the PGD performed in this dissertation are relevant for the application of the GD OES analysis in materials science. During the collaborative work with Helmholtz-Zentrum Berlin für Materialien und Energie and with the research group of Dr. Thomas Gemming at IFW Dresden the optimized pulsed GD OES measurements could be successfully applied at the investigation of thin film solar cells with CIGSe light absorbing layer and electrode matallizations of SAW devices. In case of solar cell samples pulsed GD OES depth profiling along with SIMS measurements reveal the role of the Al2O3 barrier layer in high efficiency solar cells consisting of a CIGSe/Mo/Al2O3/steel substrate layer stack (the barrier layer is to prevent the Fe diffusion into the CIGSe). The features of the CIGSe films growth are studied with help of pulsed GD OES and in situ synchrotron XRD measurements. The diffusion coefficient of Zn into the CuInS2 layer is determined for the first time from the measured GD OES depth profiles of the corresponding solar cell samples. In case of SAW samples, pulsed GD OES measurements helped to evaluate the different SAW electrode preparation procedures and to select the most suitable one. In addition pulsed GD OES depth profiling along with XPS, TEM-EDX and electrode lifetime measurements indicate the possible mechanism of power durability and lifetime improvement of the SAW devices when a small amount of Al is added to the Cu-based electrodes. / Die optische Glimmentladungsspektroskopie (engl. Glow Discharge Optical Emission Spectrometry - GD OES) hat sich als eine vielfältige und schnelle Methode für die direkte Analyse von festen Materialien erwiesen. Die Anwendung von gepulsten Glimmentladungen (GD) bietet eine Reihe von Vorteilen im Vergleich zu einer kontinuierlichen Entladung und erweitert dadurch das analytische Potential der Methode. Die praktische Anwendung von gepulsten GD erfordert jedoch ein tiefes Verständnis der Prozesse, die in der Entladung und im elektrischen System ablaufen. Der Einfluss der Puls- und Plasmaparameter auf die analytische Leistung der gepulsten GD ist bislang noch nicht umfassend erforscht worden. Die Zielstellung dieser Arbeit besteht in der Untersuchung der Eigenschaften der gepulsten GD, welche von besonderer Bedeutung sowohl für das Verständnis des Entladungsprozesses als auch für analytische Anwendungen ist. Die Auswirkungen der Pulsparameter auf die gepulste GD wurde für den Gleichstrom-(DC) und Hochfrequenz- (HF) Modus untersucht und verglichen. Die Reihenfolge der Untersuchungen wurde in dieser Arbeit wie folgt gewählt: elektrische Parameter, Sputterkraterformen, Sputterraten und Lichtemission. Die Form des Sputterkraters korreliert stark mit der Pulsdauer, selbst wenn das Tastverhältnis konstant ist. Die Pulsdauer beeinflusst nicht nur die Kraterform, sondern auch die Intensität der Emissionslinien (bei konstantem Tastverhältnis). Darüber hinaus ist dieser Einfluss unterschiedlich für Atome und Ionen. Dieses Verhalten wurde an mehreren Emissionslinien (atomar bzw. ionisch) nachgewiesen. Aus der Analyse der U-I-Kennlinien der gepulsten GD ergab sich, dass es zu einer Erhitzung des Plasmas bei höherem Tastverhältnis kommt. Dieser Effekt wurde zur Bestimmung der Plasma-Gastemperatur ausgenutzt. Die ermittelten Temperaturen wurden mit einer andere Methode verglichen. Aus der Abschätzung ergab sich, dass die Plasmatemperatur bei gepulsten GD um bis zu 100 K gesenkt werden und durch die Pulsparameter genauer eingestellt werden kann. Der Einfluss des Sputterns auf Cu(In,Ga)Se2 (CIGSe) Dünnschichten von Solarzellen wurde erstmals beschrieben. REM-Untersuchungen an GD-gesputterten CIGSe Schichten haben gezeigt, dass die Sputtereffekte durch die Variation der Pulsparameter reduziert werden können. Es konnte gezeigt werden, dass HF- und DC-Entladungen dieselben Effekte aufweisen und sich nur geringfügig voneinander unterscheiden. Daraus kann geschlussfolgert werden, dass DC- und HF-Entladungen in Bezug auf elektrische Eigenschaften, Kraterformen, Lichtemission und Temperatur sehr ähnlich sind. Die Quantifizierung der mit gepulsten GD gemessenen Tiefenprofile ergab ferner, dass die Anwendung der Quantifizierungsmethoden für den kontinuierlichen Modus unter den gegebenen Bedingungen zulässig ist. Die Tiefenprofile von Solarzellen-Schichten sowie SAW-Metallisierungen wurden anhand gepulster GD gemessen und quantifiziert. Die empfohlenen Quantifizierungsmethoden können mit kommerziellen GD OES-Geräten durchgeführt werden. Die Untersuchungen an gepulsten GD sind insbesondere relevant für GD OES-Anwendungen im Bereich der Werkstoffwissenschaft. Während der Zusammenarbeit mit dem Helmholtz-Zentrum Berlin für Materialien und Energie und der Arbeitsgruppe von Dr. Thomas Gemming (IFW Dresden) konnten optimierte, gepulste GD OES Messungen erfolgreich zur Untersuchung von Dünnschicht-Solarzellen bzw. hochleistungsbeständigen SAW-Metallisierungen angewendet werden. Für die Solarzellen haben GD OES und SIMS Messungen geholfen, die Rolle der Al2O3-Barriere in CIGSe/Mo/Al2O3 Schichtstapeln auf flexiblem Stahlsubstrat besser zu verstehen (Al2O3 soll die Diffusion der Fe-Atome in CIGSe verhindern). Die gemeinsame Untersuchung getemperter CIGSe-Schichten mit gepulster GD OES und in-situ Synchrotron-XRD ergab neue Erkenntnisse zum Schichtwachstum. Der Diffusionskoeffizient von Zn in CuInS2 wurde erstmals aus GD OES-Tiefenprofilen bestimmt. Im Fall der SAW-Metallisierungen konnte die GD OES zur Bestimmung des geeignetsten Herstellungsverfahrens einen wichtigen Beitrag leisten. Die gepulste GD OES hat neben anderen Untersuchungsmethoden wie TEM-EDX, XPS und Lebensdauermessungen die Verbesserung der Leistungsbeständigkeit von Cu-Metallisierungen durch geringen Al-Zusatz aufklären können.

This thesis presents experimental studies of low-temperature atmospheric pressure plasma sources with generic ability to effectively treat large-scale three-dimensional (3D) objects. The reported large-scale plasma sources are developed through parallelisation of single plasma jets. This strategy outshines the other reported strategies for treatment of uneven surfaces by being able to produce spatially extended plasma directly onto the surface of heavily three-dimensional objects. Comparable studies of the design of elemental plasma jets bring out a hybrid electrode configuration, the capillary-ring jet, as the best elemental jet to be used in the parallelisation. It is found that the introduction of a ballast resistor to the individual jet circuit or built-in capacitance is important to assure the jet-to-jet synchronism, stability and uniformity. Electrical and optical analyses of one-dimensional (1D) array of atmospheric pressure plasma jets demonstrate robust temporal and spatial jet-to-jet uniformity both for flat and sloped surfaces. Hexagonally-arranged two-dimensional (2D) arrays of atmospheric pressure plasma jets show good level of insusceptibility to variations of the downstream samples in their physical dimensions as well as structural and material properties. The reaction chemistry impact area of a 2D 37-jet array is estimated to be 18.6 cm2. These confirm the plasma jet arrays as a viable option as large-scale atmospheric plasma sources, well suited for many processing applications including plasma medicine. The spatially separated dual-frequency excitation further benefits the plasma jet in that separate control of different important plasma parameters is possible. Enhanced plasma properties achieved by the dual-frequency offer greater potential to the jet arrays.

Silício amorfo hidrogenado depositado por descarga luminescente tem adquirido posição de destaque entre os vários materiais foto-sensíveis, principalmente devido à sua fácil obtenção e versatilidade em propriedades. Neste trabalho, preparamos amostras de a-Si:H (Silício amorfo hidrogenado) utilizando o método de descarga de RF em atmosfera de gás SiH4, utilizando como substrato vidro e silício cristalino. As amostras depositadas sobre vidro foram utilizadas para estudo de formação de defeitos meta-estáveis no filme morfo devido a exposição à Raios-X. Os mecanismos de formação e recuperação dos defeitos foram analisados através do estudo da fotocondutividade, revelando a possível natureza de tais defeitos. Acreditamos que se trata da quebra de ligações Si-H e Si-Si, formando armadilhas para elétrons condutores. Analisamos a resposta espectral da fotocondutividade e absorção óptica, que forneceram informações a respeito do gap óptico do material. As amostras preparadas sobre c-Si foram utilizadas para a espectroscopia no infra-vermelho, onde analisamos o espectro das vibrações no material, bem como procuramos evidências da existência de hidrogênio molecular. / Hydrogenated amorphous silicon deposited by the glow discharge technique has been prominent among several photosensitive materials, mainly due to their easy obtention process and versatile properties. In this work, we have prepared hydrogenated amorphous silicon (a-Si:H) samples using the RF discharge method in SiH gaseous atmosphere. We have used glass and crystalline silicon as substrate. The samples which were deposited on glasses were used for the study on the creation of metastables defects in amorphous films due to X-Ray exposition. The creation and annealing process were analyzed through photoconductivity measurements which showed the possible origin of such defects. We believe that this behavior takes place due the breaking of Si-Si and Si-H bounds, which build up traps for free electrons. We have analyzed the photoconductivity spectral response and the optical absorption which give us information about the optical gap of this material. The samples which were prepared on crystalline silicon materials were used for infra-red spectroscopy, were we have analyzed the vibration spectra of a-Si:H, and also have been looking for evidences about the existence of molecular hydrogen.

The field of ambient desorption/ionization mass spectrometry (ADI-MS) has existed for over a decade. ADI-MS is a technique that offers benefits including fast analysis time, simple ionization sources that are easily constructed, and little to no required sample preparation. The research presented here describes efforts to better understand plasma-based ADI-MS sources and to explore the use of hydrogen-doped plasma gases with these sources. The use of hydrogen-doped argon (H2/Ar) and hydrogen-doped helium (H2/He) as plasma gases for a dielectric barrier discharge (DBD) and an AC glow discharge is presented first. When using the DBD, the intensity of the signal obtained when analyzing organic molecules in positive ion mode was increased by factors up to 37 times. In negative ion mode, only H2/Ar was shown to enhance the signal of an organic analyte. The limits of detection for caffeine when using hydrogen-doped plasma gases were found to decrease by factors of 78 and 1.9 for H2/Ar and H2/He respectively. The same phenomenon was observed when using H2/Ar with the AC discharge, but no signal enhancement was observed when using hydrogen-doped helium with the AC discharge. Similarly, if the DBD was allowed to ground through a wire rather than through the air, no signal enhancement was observed for H2/He. Using H2/Ar with metal samples is presented second. By using the metal sample as the grounded electrode for the AC glow discharge, many different metals could be detected directly with a time-of-flight mass spectrometer (TOF-MS) in the form of atomic ions both on their own and in combination with water and ammonia from the discharge. Any refractory metals tested did not yield signal. In addition to direct analysis with a TOF-MS, the AC discharge was used as a sampling method for an inductively coupled plasma mass spectrometer (ICP-MS). When coupled with an ICP-MS, the AC glow discharge was found capable of sampling even refractory elements, though the power of the ICP was required for ionization and detection. Scanning electron microscope (SEM) images of a copper surface exposed to the plasma discharge showed signs of melting when using the H2/Ar. Finally, a computer simulation of the chemistry and flow dynamics of a DC glow discharge generated in helium is presented. The simulation explores many of the fundamental processes at work and how they depend on the composition of the plasma gas. The generation of important species in the plasma was found to depend more on the amount of N2 and H2O impurities in the plasma gas rather than on the humidity or air pressure.