Köln, Universiẗat, Diss., 2003. / Dateiformat: tgz, Datei im PDF-Format.

Erlangen, Nürnberg, Universiẗat, Diss., 2004.

Techn. University, Diss.--Hamburg-Harburg, 2004. / Zsfassung in dt. Sprache.

Es wurden neue unkonventionelle Wege zur Herstellung kostengünstiger Kohlenstoffkompositmembranen untersucht, welche in Spezialgebieten der Membrantechnik zur Filtration aggressiver Flüssigmedien hätten eingesetzt werden können. Als Ausgangsmaterialien kamen sowohl für den Trägerkörper und die Zwischenschicht als auch für die Trennschicht Cellulose bzw. cellulosehaltige Materialien zum Einsatz, deren Kohlenstoffausbeuten durch thermogravimetrische Analyse (TGA) bestimmt wurden. Zum Zwecke der Trennschichtpräparation wurden diese in geeigneten organischen Lösungsmitteln gelöst. Darüber hinaus wurden erstmals anorganische Salzhydratschmelzen sowie wäßrige Salz-Wasser-Systeme zum Aktivieren, Lösen oder Suspendieren der Cellulose eingesetzt. Das Aufbringen der Celluloselösungen auf dem Trägerkörper erfolgte durch Tauchen, Sprühen, Rakeln und Infiltration. Zur Charakterisierung der erhaltenen Membranen kamen vor allem die Raseterelektronenmikroskopie (REM) gekoppelt mit EDX und die Kapillarfluß-Porosimetrie (CFP) zum Einsatz.

Für die hochselektive technische Trennung von Stoffen hält die Natur eine optimale Lösung namens Zeolithe bereit. In dieser Arbeit wurden Zeolith 4A in Form von Partikeln und wenig permeables Polymer in einer Membran kombiniert. Die Partikel lagen dabei in einer Monolage vor und wurden lediglich seitlich vom Polymer eingefasst, sodass sie beide Oberflächen der Polymerschicht durchbrachen. Diese Einbettung zu so genannten Zeolithkompositmembranen erlaubt einen Stofftransport ausschließlich durch die hochselektiven Zeolithpartikel. Die Herstellung und Charakterisierung der Zeolithkompositmembranen stehen im Mittelpunkt der vorliegenden Arbeit. Für die Membranherstellung kam das Prinzip der partikelassistierten Benetzung einer Wasseroberfläche zum Einsatz. Hierfür wurden die Zeolithpartikel beschichtet und anschließend das unverändert zugängliche Porensystem mittels Thermogravimetrie in Wasseradsorptions-Desorptionsmessungen nachgewiesen. Aus beschichteten Partikeln und passendem Monomer konnten schichtdickenoptimierte Zeolithkompositmembranen hergestellt werden. Es wurde eine Permeabilität P für Wasserdampf von 49 barrer festgestellt, während die Gase Stickstoff und Sauerstoff keinen Transportnachweis zuließen (P < 0,03 barrer). Daraus ergeben sich Selektivitäten von über 1600. Die Durchlässigkeit für Wasser beweist ein offenes Porensystem, die Impermeabilität für Stickstoff und Sauerstoff deutet auf eine sehr geringe Defektdichte hin, was beste Voraussetzungen für Trennmembranen darstellt. Das Herstellungsprinzip soll als Vorlage für die Präparation maßgeschneiderter Kompositmembranen mit wählbarer Porengröße dienen. Vergleiche zu konventionellen Zeolithmembranen belegen, dass die partikelassistierte Benetzung die Methode der Wahl ist, partikelförmiges hochselektives Material optimal einzubetten, ohne die begehrten Permeationseigenschaften zu beeinträchtigen. / An optimal material for highly selective separation processes can be found in zeolites. We prepared composite membranes composed of zeolite 4A particles and a polymer of low permeability. The particles formed a dense monolayer which were embedded into the polymer sheet in such a way that each particle prenetrates both the top and the bottom surface of the sheet. Only this embedding offffers a transport through the highly selective particles exclusively. This work focusses on these so called zeolite composite membranes, on their preparation and characterization. The preparation of the membranes was done via particle assisted wetting on a water surface. Therefore the zeolite particles were coated by a suitable silane agent and a blocking of the pore openings by the coating process was disproved by water adsorption-desorption measurements via TGA. Using the coated particles and a suitable monomer composite membranes could be formed and the optimum thickness was found. The membranes were permeable for water vapor (permeability P = 49 barrer), but impermeable for nitrogen and oxygene (P < 0,03 barrer (detection limit)). This results in a selectivity of above 1600. The permeability for water indicates that the molecules are transported through the zeolite channels. The impermeability for nitrogene and oxygene indicates a very low amount of defects. Furthermore the composite nature of the membrane reduces brittleness thus rendering it a promising candidate for separation technology with tailoring the pore size.

Es wurden neue unkonventionelle Wege zur Herstellung kostengünstiger Kohlenstoffkompositmembranen untersucht, welche in Spezialgebieten der Membrantechnik zur Filtration aggressiver Flüssigmedien hätten eingesetzt werden können. Als Ausgangsmaterialien kamen sowohl für den Trägerkörper und die Zwischenschicht als auch für die Trennschicht Cellulose bzw. cellulosehaltige Materialien zum Einsatz, deren Kohlenstoffausbeuten durch thermogravimetrische Analyse (TGA) bestimmt wurden. Zum Zwecke der Trennschichtpräparation wurden diese in geeigneten organischen Lösungsmitteln gelöst. Darüber hinaus wurden erstmals anorganische Salzhydratschmelzen sowie wäßrige Salz-Wasser-Systeme zum Aktivieren, Lösen oder Suspendieren der Cellulose eingesetzt. Das Aufbringen der Celluloselösungen auf dem Trägerkörper erfolgte durch Tauchen, Sprühen, Rakeln und Infiltration. Zur Charakterisierung der erhaltenen Membranen kamen vor allem die Raseterelektronenmikroskopie (REM) gekoppelt mit EDX und die Kapillarfluß-Porosimetrie (CFP) zum Einsatz.

Für die hochselektive technische Trennung von Stoffen hält die Natur eine optimale Lösung namens Zeolithe bereit. In dieser Arbeit wurden Zeolith 4A in Form von Partikeln und wenig permeables Polymer in einer Membran kombiniert. Die Partikel lagen dabei in einer Monolage vor und wurden lediglich seitlich vom Polymer eingefasst, sodass sie beide Oberflächen der Polymerschicht durchbrachen. Diese Einbettung zu so genannten Zeolithkompositmembranen erlaubt einen Stofftransport ausschließlich durch die hochselektiven Zeolithpartikel. Die Herstellung und Charakterisierung der Zeolithkompositmembranen stehen im Mittelpunkt der vorliegenden Arbeit. Für die Membranherstellung kam das Prinzip der partikelassistierten Benetzung einer Wasseroberfläche zum Einsatz. Hierfür wurden die Zeolithpartikel beschichtet und anschließend das unverändert zugängliche Porensystem mittels Thermogravimetrie in Wasseradsorptions-Desorptionsmessungen nachgewiesen. Aus beschichteten Partikeln und passendem Monomer konnten schichtdickenoptimierte Zeolithkompositmembranen hergestellt werden. Es wurde eine Permeabilität P für Wasserdampf von 49 barrer festgestellt, während die Gase Stickstoff und Sauerstoff keinen Transportnachweis zuließen (P < 0,03 barrer). Daraus ergeben sich Selektivitäten von über 1600. Die Durchlässigkeit für Wasser beweist ein offenes Porensystem, die Impermeabilität für Stickstoff und Sauerstoff deutet auf eine sehr geringe Defektdichte hin, was beste Voraussetzungen für Trennmembranen darstellt. Das Herstellungsprinzip soll als Vorlage für die Präparation maßgeschneiderter Kompositmembranen mit wählbarer Porengröße dienen. Vergleiche zu konventionellen Zeolithmembranen belegen, dass die partikelassistierte Benetzung die Methode der Wahl ist, partikelförmiges hochselektives Material optimal einzubetten, ohne die begehrten Permeationseigenschaften zu beeinträchtigen. / An optimal material for highly selective separation processes can be found in zeolites. We prepared composite membranes composed of zeolite 4A particles and a polymer of low permeability. The particles formed a dense monolayer which were embedded into the polymer sheet in such a way that each particle prenetrates both the top and the bottom surface of the sheet. Only this embedding offffers a transport through the highly selective particles exclusively. This work focusses on these so called zeolite composite membranes, on their preparation and characterization. The preparation of the membranes was done via particle assisted wetting on a water surface. Therefore the zeolite particles were coated by a suitable silane agent and a blocking of the pore openings by the coating process was disproved by water adsorption-desorption measurements via TGA. Using the coated particles and a suitable monomer composite membranes could be formed and the optimum thickness was found. The membranes were permeable for water vapor (permeability P = 49 barrer), but impermeable for nitrogen and oxygene (P < 0,03 barrer (detection limit)). This results in a selectivity of above 1600. The permeability for water indicates that the molecules are transported through the zeolite channels. The impermeability for nitrogene and oxygene indicates a very low amount of defects. Furthermore the composite nature of the membrane reduces brittleness thus rendering it a promising candidate for separation technology with tailoring the pore size.

The combination of modern self-assembly techniques with well-established top-down processing methods pioneered in the electronics industry is paving the way for increasingly sophisticated devices in the future[1]. Nanomembranes, made from a variety of materials, can provide the necessary framework for a diverse range of device structures incorporating wrinkling, buckling, folding, and rolling of thin films[2, 3]. Over the past decade, an elegant symbiosis of bottom-up and top-down methods has been developed, allowing the fabrica- tion of hybrid layer systems via the controlled release and rearrangement of inherently strained layers [4]. Self-assembled rolled-up structures[4, 5] have become increasingly at- tractive in a number of fields including micro/nano uidics[6], optics[7](including metama- terial optical fibers[8]), Lab on a Chip applications[9], and micro- and nanoelectronics[10]. The use of such structures for microelectronic applications has been driven by the versatility in contacting geometries and the abundance of material combinations that these devices offer. By allowing devices to expand in the third dimension, certain obstacles that inhibit 2D structuring can be overcome in elegant ways. Similarly, recent progress in nanostructured superconducting electronic structures has been receiving increased attention[11]. The advancement of such devices has been mo- tivated by their use in quantum computation[12], high sensitivity radiation sensors[13], precision voltage standards[14] and superconducting spintronics[15] to name a few. Combining semiconductor with superconductor materials to create new hybrid geometries is advantageous because it adds the functionalities of the semiconductor, including high charge carrier mobilities, gating possibilities, and refined processing technologies. The main focus of the work presented in this thesis is the development of new methods for controlling strain behavior and its applications toward novel semiconduc- tor/superconductor heterostructures based on nanomembranes. More specifically, the goal is to integrate inherently strained semiconductor layer structures with superconducting materials to create innovative electronic devices by the controlled releasing and rearrangement of thin films. By rolling up pre-patterned semiconductor/superconductor layers, device geometries have been realized that are not feasible using any other technique. In this way, superconducting hybrid junctions, or Josephson junctions, have been created and their basic properties investigated. The Josephson effect, and junctions displaying this quantum coherent behavior, have found many essential uses in diverse areas of science and technology. Many research groups around the world are involved in finding new materials and fabrication methods to tune the properties and structure of such Josephson devices further[11]. The inclusion of semi- conductors, for example, allows for a greater control of the charge carrier density within the junction area, thus allowing for "transistor-like" behavior in these superconducting devices. By rolling up the superconductor contacts using a strained semiconductor as scaffolding, the fabrication of hybrid nano-junctions is simplified drastically, removing the need for complicated processing steps such as electron-beam or nano-imprint lithography. Furthermore, the technique allows many nanometer-sized devices to be created in parallel on a single chip which has the advantage that it can be scaled up to full-wafer processing. First, post-growth processing techniques of epitaxial layers are developed in order to extend the control of hybrid device fabrication. Here, three unique concepts for controlling the rolling behavior of strained semiconductor nanomembranes are presented. First an optical method for inhibiting the rolling of the strained layers is described. Next, a selective etching method for destroying the inherent strain within the semiconductor layer is introduced. Finally, a method by which the strain gradient across a trilayer stack is altered in situ during rolling is presented. Next, the fabrication of a hybrid nanomembrane-based superconducting device is presented. Various experimental details of the fabrication process are analyzed, and the electronic properties of the completed device are investigated. The devices created here highlight the fabrication process in which nanometer-sized structures are created using self-assembly techniques and standard microelectronics fabrication methods, presenting a new method to circumvent more complicated processing techniques. References [1] G. M. Whitesides and B. Grzybowski. Self-assembly at all scales. Science 295, 2418{2421 (2002). [2] Y. G. Sun, W. M. Choi, H. Q. Jiang, Y. G. Y. Huang and J. A. Rogers. Controlled buckling of semiconductor nanoribbons for stretchable electronics. Nature Nanotechnology 1, 201{207 (2006). [3] O. G. Schmidt and K. Eberl. Nanotechnology - Thin solid films roll up into nanotubes. Nature 410, 168 (2001). [4] O. G. Schmidt, C. Deneke, Y. Nakamura, R. Zapf-Gottwick, C. Mller and N. Y. Jin-Phillipp. Nanotechnology { Bottom-up meets top-down. Advanced Solid State Physics 42, 231 (2002). [5] V. Ya. Prinz, V. A. Seleznev, A. K. Gutakovsky, A. V. Chehovskiy, V. V. Preobrazhenskii, M. A. Putyato and T. A. Gavrilova. Free-standing and overgrown InGaAs/GaAs nanotubes, nanohelices and their arrays. Physica E 6, 828 (2000). [6] D. J. Thurmer, C. Deneke, Y. F. Mei and O. G. Schmidt. Process integration of microtubes for uidic applications. Applied Physics Letters 89, 223507 (2006). [7] R. Songmuang, A. Rastelli, S. Mendach and O. G. Schmidt. SiOx/Si radial superlattices and microtube optical ring resonators. Applied Physics Letters 90, 091905 (2007). [8] E. J. Smith, Z. W. Liu, Y. F. Mei and O. G. Schmidt. Combined surface plasmon and classical waveguiding through metamaterial fiber design. Nano Letters 10, 1{5 (2010). [9] G. S. Huang, Y. F. Mei, D. J. Thurmer, E. Coric and O. G. Schmidt. Rolled-up transparent microtubes as two-dimensionally confined culture scaffolds of individual yeast cells. Lab on a Chip 9, 263{268 (2009). [10] C. C. B. Bufon, J. D. C. Gonzalez, D. J. Thurmer, D. Grimm, M. Bauer and O. G. Schmidt. Self-assembled ultra-compact energy storage elements based on hybrid nanomembranes. Nano Letters 10, 2506{2510 (2010). [11] G. Katsaros, P. Spathis, M. Stoffel, F. Fournel, M. Mongillo, V. Bouchiat, F. Lefloch, A. Rastelli, O. G. Schmidt and S. De Franceschi. Hybrid superconductor-semiconductor devices made from self-assembled SiGe nanocrystals on silicon. Nature Nanotechnology 5, 458{464 (2010). [12] Y. J. Doh, J. A. van Dam, A. L. Roest, E. P. A. M. Bakkers, L. P. Kouwenhoven and S. De Franceschi. Tunable supercurrent through semiconductor nanowires. Science 309, 272{275 (2005). [13] F. Giazotto, T. T. Heikkila, G. P. Pepe, P. Helisto, A. Luukanen and J. P. Pekola. Ultrasensitive proximity Josephson sensor with kinetic inductance readout. Applied Physics Letters 92, 162507 (2008). [14] S. P. Benz. Superconductor-normal-superconductor junctions for programmable voltage standards. Applied Physics Letters 67, 2714{2716 (1995). [15] Y. C. Tao and J. G. Hu. Superconducting spintronics: Spin-polarized transport in superconducting junctions with ferromagnetic semiconducting contact. Journal of Applied Physics 107, 041101 (2010).

Gegenstand dieser Arbeit ist es, die Temperaturbeständigkeit von bikontinuierlichen Kompositmembranen bestehend aus Zeolith 4A und Visiomer HEMATMDI zu überprüfen und das Verhalten ihrer Permeanz im Verlauf der Temperaturerhöhung zu untersuchen. Weiterhin wird ihre Verwendbarkeit für technisch und industriell relevante Prozesse der Gastrocknung nachgewiesen. Zunächst wird thermogravimetrisch untersucht, bei welcher Temperatur Zersetzungserscheinungen an der polymeren Komponente auftreten. Anschließend wird thermogravimetrisch der Wassergehalt von Zeolith 4A im Bereich dieser Temperatur bestimmt. Hierauf folgen Permeationsmessungen mit Sauerstoff und Stickstoff an der bikontinuierlichen Kompositmembran. Die Temperatur wird hierbei schrittweise bis knapp unter die Zersetzungstemperatur des Polymers erhöht. Die Eignung der Membranen zur Gastrocknung wird exemplarisch an der Trocknung von Erdgas gezeigt. Es werden die Permeanzen für Wasserdampf und Methan als Hauptbestandteil von Erdgas mittels Einzelgasmessungen experimentell bestimmt. Aus diesen Permeanzen errechnet sich die ideale Selektivität der bikontinuierlichen Kompositmembran von Wasserdampf gegenüber Methan. Mit ihrer Hilfe lässt sich die Eignung der Membran zur Trocknung von Erdgas abschätzen. / The aim of this work is to study the temperature resistance of bicontinuous composite membranes, composed zeolite 4A and Visiomer HEMATMDI, and their permeances with rising temperatures. Furthermore their suitability for gas drying is investigated.

The combination of modern self-assembly techniques with well-established top-down processing methods pioneered in the electronics industry is paving the way for increasingly sophisticated devices in the future[1]. Nanomembranes, made from a variety of materials, can provide the necessary framework for a diverse range of device structures incorporating wrinkling, buckling, folding, and rolling of thin films[2, 3]. Over the past decade, an elegant symbiosis of bottom-up and top-down methods has been developed, allowing the fabrica- tion of hybrid layer systems via the controlled release and rearrangement of inherently strained layers [4]. Self-assembled rolled-up structures[4, 5] have become increasingly at- tractive in a number of fields including micro/nano uidics[6], optics[7](including metama- terial optical fibers[8]), Lab on a Chip applications[9], and micro- and nanoelectronics[10]. The use of such structures for microelectronic applications has been driven by the versatility in contacting geometries and the abundance of material combinations that these devices offer. By allowing devices to expand in the third dimension, certain obstacles that inhibit 2D structuring can be overcome in elegant ways. Similarly, recent progress in nanostructured superconducting electronic structures has been receiving increased attention[11]. The advancement of such devices has been mo- tivated by their use in quantum computation[12], high sensitivity radiation sensors[13], precision voltage standards[14] and superconducting spintronics[15] to name a few. Combining semiconductor with superconductor materials to create new hybrid geometries is advantageous because it adds the functionalities of the semiconductor, including high charge carrier mobilities, gating possibilities, and refined processing technologies. The main focus of the work presented in this thesis is the development of new methods for controlling strain behavior and its applications toward novel semiconduc- tor/superconductor heterostructures based on nanomembranes. More specifically, the goal is to integrate inherently strained semiconductor layer structures with superconducting materials to create innovative electronic devices by the controlled releasing and rearrangement of thin films. By rolling up pre-patterned semiconductor/superconductor layers, device geometries have been realized that are not feasible using any other technique. In this way, superconducting hybrid junctions, or Josephson junctions, have been created and their basic properties investigated. The Josephson effect, and junctions displaying this quantum coherent behavior, have found many essential uses in diverse areas of science and technology. Many research groups around the world are involved in finding new materials and fabrication methods to tune the properties and structure of such Josephson devices further[11]. The inclusion of semi- conductors, for example, allows for a greater control of the charge carrier density within the junction area, thus allowing for "transistor-like" behavior in these superconducting devices. By rolling up the superconductor contacts using a strained semiconductor as scaffolding, the fabrication of hybrid nano-junctions is simplified drastically, removing the need for complicated processing steps such as electron-beam or nano-imprint lithography. Furthermore, the technique allows many nanometer-sized devices to be created in parallel on a single chip which has the advantage that it can be scaled up to full-wafer processing. First, post-growth processing techniques of epitaxial layers are developed in order to extend the control of hybrid device fabrication. Here, three unique concepts for controlling the rolling behavior of strained semiconductor nanomembranes are presented. First an optical method for inhibiting the rolling of the strained layers is described. Next, a selective etching method for destroying the inherent strain within the semiconductor layer is introduced. Finally, a method by which the strain gradient across a trilayer stack is altered in situ during rolling is presented. Next, the fabrication of a hybrid nanomembrane-based superconducting device is presented. Various experimental details of the fabrication process are analyzed, and the electronic properties of the completed device are investigated. The devices created here highlight the fabrication process in which nanometer-sized structures are created using self-assembly techniques and standard microelectronics fabrication methods, presenting a new method to circumvent more complicated processing techniques. References [1] G. M. Whitesides and B. Grzybowski. Self-assembly at all scales. Science 295, 2418{2421 (2002). [2] Y. G. Sun, W. M. Choi, H. Q. Jiang, Y. G. Y. Huang and J. A. Rogers. Controlled buckling of semiconductor nanoribbons for stretchable electronics. Nature Nanotechnology 1, 201{207 (2006). [3] O. G. Schmidt and K. Eberl. Nanotechnology - Thin solid films roll up into nanotubes. Nature 410, 168 (2001). [4] O. G. Schmidt, C. Deneke, Y. Nakamura, R. Zapf-Gottwick, C. Mller and N. Y. Jin-Phillipp. Nanotechnology { Bottom-up meets top-down. Advanced Solid State Physics 42, 231 (2002). [5] V. Ya. Prinz, V. A. Seleznev, A. K. Gutakovsky, A. V. Chehovskiy, V. V. Preobrazhenskii, M. A. Putyato and T. A. Gavrilova. Free-standing and overgrown InGaAs/GaAs nanotubes, nanohelices and their arrays. Physica E 6, 828 (2000). [6] D. J. Thurmer, C. Deneke, Y. F. Mei and O. G. Schmidt. Process integration of microtubes for uidic applications. Applied Physics Letters 89, 223507 (2006). [7] R. Songmuang, A. Rastelli, S. Mendach and O. G. Schmidt. SiOx/Si radial superlattices and microtube optical ring resonators. Applied Physics Letters 90, 091905 (2007). [8] E. J. Smith, Z. W. Liu, Y. F. Mei and O. G. Schmidt. Combined surface plasmon and classical waveguiding through metamaterial fiber design. Nano Letters 10, 1{5 (2010). [9] G. S. Huang, Y. F. Mei, D. J. Thurmer, E. Coric and O. G. Schmidt. Rolled-up transparent microtubes as two-dimensionally confined culture scaffolds of individual yeast cells. Lab on a Chip 9, 263{268 (2009). [10] C. C. B. Bufon, J. D. C. Gonzalez, D. J. Thurmer, D. Grimm, M. Bauer and O. G. Schmidt. Self-assembled ultra-compact energy storage elements based on hybrid nanomembranes. Nano Letters 10, 2506{2510 (2010). [11] G. Katsaros, P. Spathis, M. Stoffel, F. Fournel, M. Mongillo, V. Bouchiat, F. Lefloch, A. Rastelli, O. G. Schmidt and S. De Franceschi. Hybrid superconductor-semiconductor devices made from self-assembled SiGe nanocrystals on silicon. Nature Nanotechnology 5, 458{464 (2010). [12] Y. J. Doh, J. A. van Dam, A. L. Roest, E. P. A. M. Bakkers, L. P. Kouwenhoven and S. De Franceschi. Tunable supercurrent through semiconductor nanowires. Science 309, 272{275 (2005). [13] F. Giazotto, T. T. Heikkila, G. P. Pepe, P. Helisto, A. Luukanen and J. P. Pekola. Ultrasensitive proximity Josephson sensor with kinetic inductance readout. Applied Physics Letters 92, 162507 (2008). [14] S. P. Benz. Superconductor-normal-superconductor junctions for programmable voltage standards. Applied Physics Letters 67, 2714{2716 (1995). [15] Y. C. Tao and J. G. Hu. Superconducting spintronics: Spin-polarized transport in superconducting junctions with ferromagnetic semiconducting contact. Journal of Applied Physics 107, 041101 (2010).