Zugl.: Paderborn, Univ., Diss., 2008

In this thesis, new all-printed capacitors are developed for the applications of energy storage, filter, and resonant circuits by using new dielectric material and an advanced technology. The innovative devices provide satisficing electrical performances with high breakdown voltages and capacitance densities. The main body of this thesis is divided in three parts. The first part is to introduce the fundamental background of printing technologies, electrical capacitors and printable materials. Among all the printing technologies, direct writing family is the most advantageous in the small-scale and fast production of printed electronics due to the properties of masterless processing, digital control, and print-on-demand. Both inkjet printing and ultrasonic fluid dispensing applied in this work are grouped into the direct writing family. A cross-linkable dielectric material poly(methyl methacrylate)84/(4-benzoylphenyl methacrylate)16 [P(MMA84/BPMA16)] exhibits the optimized chemical and mechanical stabilities in comparison with uncross-linked poly(methyl methacrylate) (PMMA). Poly(vinylidene fluoride-co-trifluoro ethylene) [P(VDF-TrFE)] exhibits a high dielectric constant of 16. The great advantages of both polymeric dielectrics make them ideal for printed electronics. The second part is devoted to the preparation of printed thin-film capacitors by providing four different layouts and architectures for multiple electronic applications. The printing setup, process setting and steps are summarized in detail. The following part which is the major content of this thesis is divided into two aspects: in the first aspect, the intriguing new form of continuous solution dispensing technology, ultrasonic fluid dispensing, is demonstrated as an alternative printing technology for the commonly applied ones. In comparison with the widely-used inkjet printing, continuous solution dispensing is the most advantageous in thin-film capacitor processing with metal nanoparticle and polymer dielectric inks. It enables precise pattern transfers with low surface roughness, small feature size (as small as 5 μm), and accurate positioning (5 μm resolution). Most importantly, problems due to discrete droplets and nozzle clogging in inkjet printing are avoided in continuous solution dispensing. All the inks applied for printed capacitors in this work are printed successfully with this innovating technology. Direct printing on demand and rapid switching among different inks are some other attributes of this printing technology that enable high throughput. The second aspect of this part is to characterize and evaluate the fabricated capacitors. The measured values include capacitor dimension, dielectric strength, capacitance density, energy density, charge/discharge behavior and so on. In summary, this work provides not only the use of the advantageous materials P(MMA84/BPMA16) and P(VDF-TrFE) in high-performance capacitors, but also paves the way of developing thin-film capacitors with a new continuous solution dispensing technology which makes the low-cost and high-quality manufacture of printed devices possible.

In this thesis, new all-printed capacitors are developed for the applications of energy storage, filter, and resonant circuits by using new dielectric material and an advanced technology. The innovative devices provide satisficing electrical performances with high breakdown voltages and capacitance densities. The main body of this thesis is divided in three parts. The first part is to introduce the fundamental background of printing technologies, electrical capacitors and printable materials. Among all the printing technologies, direct writing family is the most advantageous in the small-scale and fast production of printed electronics due to the properties of masterless processing, digital control, and print-on-demand. Both inkjet printing and ultrasonic fluid dispensing applied in this work are grouped into the direct writing family. A cross-linkable dielectric material poly(methyl methacrylate)84/(4-benzoylphenyl methacrylate)16 [P(MMA84/BPMA16)] exhibits the optimized chemical and mechanical stabilities in comparison with uncross-linked poly(methyl methacrylate) (PMMA). Poly(vinylidene fluoride-co-trifluoro ethylene) [P(VDF-TrFE)] exhibits a high dielectric constant of 16. The great advantages of both polymeric dielectrics make them ideal for printed electronics. The second part is devoted to the preparation of printed thin-film capacitors by providing four different layouts and architectures for multiple electronic applications. The printing setup, process setting and steps are summarized in detail. The following part which is the major content of this thesis is divided into two aspects: in the first aspect, the intriguing new form of continuous solution dispensing technology, ultrasonic fluid dispensing, is demonstrated as an alternative printing technology for the commonly applied ones. In comparison with the widely-used inkjet printing, continuous solution dispensing is the most advantageous in thin-film capacitor processing with metal nanoparticle and polymer dielectric inks. It enables precise pattern transfers with low surface roughness, small feature size (as small as 5 μm), and accurate positioning (5 μm resolution). Most importantly, problems due to discrete droplets and nozzle clogging in inkjet printing are avoided in continuous solution dispensing. All the inks applied for printed capacitors in this work are printed successfully with this innovating technology. Direct printing on demand and rapid switching among different inks are some other attributes of this printing technology that enable high throughput. The second aspect of this part is to characterize and evaluate the fabricated capacitors. The measured values include capacitor dimension, dielectric strength, capacitance density, energy density, charge/discharge behavior and so on. In summary, this work provides not only the use of the advantageous materials P(MMA84/BPMA16) and P(VDF-TrFE) in high-performance capacitors, but also paves the way of developing thin-film capacitors with a new continuous solution dispensing technology which makes the low-cost and high-quality manufacture of printed devices possible.

Konstanz, FH, Diplomarb., 2004.

Inkjet printing has emerged from a digital graphic arts printing technology to become a versatile tool for the patterned deposition of functional materials. This thesis contributes to the research in the area of functional inkjet printing by focusing on two different topics: (i) inkjet printing of colloidal suspensions to study the principles of deposit formation and to develop deposits with photonic properties based on self-assembly, and (ii) the development of a reliable manufacturing process for all-inkjet-printed thin-film transistors, highlighting the importance of selection of materials and inks, print pattern generation, and the interplay between ink, substrate and printing conditions. (i) Colloidal suspensions containing nanospheres were applied as ink formulation in order to study the fundamental processes of layer formation and to develop structures with periodically arranged nanospheres allowing the modulation of electromagnetic waves. Evaporation-driven self-assembly was found to be the main driver for the formation of the final deposit morphology. Fine-tuning of inkjet process parameters allows the deposition of highly ordered structures of nanospheres to be arranged as monolayer, multilayer or even three-dimensional assemblies with a microscopic spherical shape. (ii) This thesis demonstrates the development of a manufacturing process for thin-film transistors based on inkjet printing. The knowledge obtained from the study with the colloidal nanospheres is used to generate homogeneous and continuous thin films that are stacked well-aligned to each other to form transistors. Industrial printheads were applied in the manufacturing process, allowing for the up-scaling of the manufacturing by printing of several thousands of devices, and thus the possibility to study the process yield as a function of printing parameters. The discrete droplet-by-droplet nature of the inkjet printing process imposes challenges on the control of printed patterns. Inkjet printing of electronic devices requires a detailed understanding about the process and all of the parameters that influence morphological or functional characteristics of the deposits, such as the selection of appropriate inks and materials, the orientation of the print pattern layout to the deposition process and the reliability of the inkjet process.

Inkjet printing has emerged from a digital graphic arts printing technology to become a versatile tool for the patterned deposition of functional materials. This thesis contributes to the research in the area of functional inkjet printing by focusing on two different topics: (i) inkjet printing of colloidal suspensions to study the principles of deposit formation and to develop deposits with photonic properties based on self-assembly, and (ii) the development of a reliable manufacturing process for all-inkjet-printed thin-film transistors, highlighting the importance of selection of materials and inks, print pattern generation, and the interplay between ink, substrate and printing conditions. (i) Colloidal suspensions containing nanospheres were applied as ink formulation in order to study the fundamental processes of layer formation and to develop structures with periodically arranged nanospheres allowing the modulation of electromagnetic waves. Evaporation-driven self-assembly was found to be the main driver for the formation of the final deposit morphology. Fine-tuning of inkjet process parameters allows the deposition of highly ordered structures of nanospheres to be arranged as monolayer, multilayer or even three-dimensional assemblies with a microscopic spherical shape. (ii) This thesis demonstrates the development of a manufacturing process for thin-film transistors based on inkjet printing. The knowledge obtained from the study with the colloidal nanospheres is used to generate homogeneous and continuous thin films that are stacked well-aligned to each other to form transistors. Industrial printheads were applied in the manufacturing process, allowing for the up-scaling of the manufacturing by printing of several thousands of devices, and thus the possibility to study the process yield as a function of printing parameters. The discrete droplet-by-droplet nature of the inkjet printing process imposes challenges on the control of printed patterns. Inkjet printing of electronic devices requires a detailed understanding about the process and all of the parameters that influence morphological or functional characteristics of the deposits, such as the selection of appropriate inks and materials, the orientation of the print pattern layout to the deposition process and the reliability of the inkjet process.:Bibliography II Abstract III Preface and acknowledgements IV On the major results and novelty of the thesis VII Table of contents VIII List of abbreviations and symbols X List of figures XII List of tables XX 1 Introduction 1 2 Fundamentals 6 2.1 Inkjet printing – an overview 6 2.2 Piezoelectric inkjet technology and a historical overview of inkjet printing 10 2.3 Pattern and film formation in inkjet printing under the scheme of self-assembly 20 2.4 Inkjet printing of colloidal nanospheres 27 2.5 Spherical colloidal assemblies 29 2.6 All-inkjet-printed thin film transistors 31 3 Experimental section 35 3.1 Inkjet printing systems and accessories 35 3.2 Inks and substrates 38 3.3 Print patterns 43 3.4 Post-processing 46 3.5 Optical, morphological and functional characterization 47 4 Inkjet printing of colloidal nanospheres: Evaporation-driven self-assembly based on ink-substrate interaction 49 4.1 Single droplet deposit morphology: Interaction of substrate and ink 49 4.2 Optical properties of inkjet-printed single droplet monolayers and multilayers 54 5 Inkjet printing of colloidal nanospheres: Evaporation-driven self-assembly of SCAs independent on substrate properties 58 5.1 Inkjet printing of spherical colloidal assemblies and their identification 58 5.2 Fine-tuning of the waveform applied to the printhead 60 5.3 Interaction of substrate and ink 66 5.4 Structures, morphologies and materials of SCAs 68 5.5 Optical properties of SCAs 76 6 Inkjet printing of TFTs: Process development and process reliability 80 6.1 Influence of print layout design 80 6.2 Selection of materials and inks 91 6.3 Manufacturing workflow and electrical TFT parameters 108 6.4 Manufacturing yields and failure origins 113 7 Summary and conclusion 124 References 127 Documentation of authorship and contribution of third persons 149 List of publications 151 APPENDIX A Formation of colloidal hemispheres on hydrophobic PTFE substrates 161 APPENDIX B Inkjet-printed higher-order cluster with N < 100 using BL280 162 APPENDIX C Inkjet-printed SCAs based on BS305 with similar sizes and inkjet-printed SCA based on PSC221 163 APPENDIX D Microreflectance spectra of SCAs and the processing of the spectra using the Savitzky-Golay filter with a second-order polynomial and a moving window of 100 data points 164 APPENDIX E Waveform, drop ejection and photographs of the printed patterns of Sun Chemical EMD5603 and UTDots UTDAgIJ1 165 APPENDIX F Smoothening of profiles obtained by profilometry of EMD5603 and UTDAgIJ1 and dependency of print resolution of layer height 166 APPENDIX G Percentage of area increase based on a 4 mm x 4 mm digital print pattern using the ink Harima NPS-JL and influence of print resolution and post-treatment temperature on sheets resistance 168 APPENDIX H Cross-sectional view of a TFT stack printed with the dielectric Sun Chemical EMD6415 that shows high layer thickness due to ink contraction after the deposition as presented in Figure 46 169 APPENDIX I Influence of printing parameters on the dielectric layer applied in the TFT 170 APPENDIX J Reduction of channel length by decreasing the S-D electrode channel length in the print pattern layout 171

Der Vortrag stellt den Aufbau und die Herstellweise gedruckter Batterien dar. Mögliche Einsatzgebiete werden diskutiert. Ferner wird die Untersuchungs- und Anwendungsvielfalt der Abteilung hinsichtlich digitaler Drucktechnologien gezeigt.

Ausgehend von der Anwendung von Folienhinterspritzprozessen für dekorative Zwecke wurde deren Nutzung für die Integration elektronischer Strukturen in Kunststoffbauteile untersucht. Die Herstellung der elektronischen Bauelemente erfolgte mittels verschiedener Druckverfahren mit elektrisch leitfähigen und dielektrischen Materialien auf Polycarbonatfolien. Im Fokus standen zum einen kapazitiv auslesbare Speicherstrukturen und zum anderen Elektrolumineszenzleuchten. Nach dem Druck wurden die bedruckten Folien z. T. verformt und hinterspritzt. In der Arbeit wird auf die Auswirkungen der Verform- und Hinterspritzprozesse eingegangen. Schwerpunktmäßig wird die elektronische bzw. optische Funktionalität der Bauelemente, die Beeinflussung durch Klimaveränderungen und die Haftfestigkeit der Folien betrachtet. Im Ergebnis konnten erstmals die Realisierbarkeit hinterspritzter elektronischer Bauelemente nachgewiesen sowie verschiedene Einflussfaktoren auf deren Funktionalität identifiziert werden. / Based on the application of film insert molding for graphic purposes, the utilization of this process for the integration of electronic devices into plastic components was examined. The manufacturing of the electronic devices was realized by applying electrical conductive and dielectric inks on polycarbonate foil by various printing processes. Capacitive data storage patterns and electroluminescent lamps are the main applications. The production sequence included the printing process, forming of the foil where required and back injection molding. The impact of forming and film insert molding was investigated. The electronic and/or optical functionality of the devices, the influence of ambient conditions like temperature or humidity and the adhesion strength of the foils were in the focus of the evaluation. As a result, the feasibility of film insert molded electronic devices could be verified and various impact factors could be identified for the first time.

Ausgehend von der Anwendung von Folienhinterspritzprozessen für dekorative Zwecke wurde deren Nutzung für die Integration elektronischer Strukturen in Kunststoffbauteile untersucht. Die Herstellung der elektronischen Bauelemente erfolgte mittels verschiedener Druckverfahren mit elektrisch leitfähigen und dielektrischen Materialien auf Polycarbonatfolien. Im Fokus standen zum einen kapazitiv auslesbare Speicherstrukturen und zum anderen Elektrolumineszenzleuchten. Nach dem Druck wurden die bedruckten Folien z. T. verformt und hinterspritzt. In der Arbeit wird auf die Auswirkungen der Verform- und Hinterspritzprozesse eingegangen. Schwerpunktmäßig wird die elektronische bzw. optische Funktionalität der Bauelemente, die Beeinflussung durch Klimaveränderungen und die Haftfestigkeit der Folien betrachtet. Im Ergebnis konnten erstmals die Realisierbarkeit hinterspritzter elektronischer Bauelemente nachgewiesen sowie verschiedene Einflussfaktoren auf deren Funktionalität identifiziert werden. / Based on the application of film insert molding for graphic purposes, the utilization of this process for the integration of electronic devices into plastic components was examined. The manufacturing of the electronic devices was realized by applying electrical conductive and dielectric inks on polycarbonate foil by various printing processes. Capacitive data storage patterns and electroluminescent lamps are the main applications. The production sequence included the printing process, forming of the foil where required and back injection molding. The impact of forming and film insert molding was investigated. The electronic and/or optical functionality of the devices, the influence of ambient conditions like temperature or humidity and the adhesion strength of the foils were in the focus of the evaluation. As a result, the feasibility of film insert molded electronic devices could be verified and various impact factors could be identified for the first time.

Die vorliegende Arbeit ist eine Untersuchung, inwieweit die Herstellung eines kartonbasierter POCT mit Kapillaren zum Transport von Flüssigkeiten mit Hilfe von Nanocellulose und additiv gefertigten Prägewerkzeugen möglich ist. Die Nanocellulose wurde von RISE aus Schweden zur Verfügung gestellt. Rheologische Untersuchungen ergaben, dass diese mit Hilfe eines Bingham-Modells beschrieben werden können und einer Fließgrenze unterliegen. Die Nanocellulose wurde mit Hilfe der konventionellen direkten Druckverfahren Flexo-, Tief- und Siebdruck auf verschiedene Kartonsorten aufgetragen. Der Flexo- und Tiefdruck erwies sich aufgrund einer Saffman-Taylor-Instabilität als ungeeignet zur Erzeugung von homogenen Schichten. Verschiedene Untersuchungen zeigten, dass mit Hilfe des Siebdrucks unter Verwendung eines Siebs mit sehr hoher Nassfarbschichtdicke die besten Ergebnisse erzielt werden konnten. Die Nutzung von offenen Kapillaren in POCT erfordert einen möglichst geringen Kontaktwinkel. Durch das Applizieren von Nanocellulose konnte sowohl der Kontaktwinkel des Kartons auf einen geeigneten Wert reduziert werden als auch das Penetrationsverhalten insofern verändert werden, dass die Penetration einer aufgetragenen Flüssigkeit zunächst in der Nanocellulose stattfindet. Die Penetration in den Karton selbst wurde durch die Nanocellulose stark verzögert. Die Funktionalität von offenen Kapillaren konnte im Rahmen dieser Arbeit aufgrund von mangelnder Herstellgenauigkeit der additiven Fertigung und begrenzter Kartonauswahl nicht erreicht werden. Allerdings konnten mit Hilfe einer Folienkaschierung funktionelle geschlossene Kapillaren erzeugt werden, welche einen Flüssigkeitstransport durch Kapillarkräfte über eine Distanz von 25 mm ohne Penetration in den Karton ermöglichen. Dies zeigt, dass die Herstellung und Nutzung von kartonbasierten POCT theoretisch möglich ist.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge / The present work is an investigation into the potential of fabricating a cardboard-based POCT with capillaries for transporting fluids using nanocellulose and additive manufactured embossing tools. The nanocellulose was provided by RISE from Sweden. Rheological studies showed that they can be described using a Bingham model and are subject to a yield point. The nanocellulose was applied to various types of cardboard using the conventional direct printing processes of flexographic, gravure and screen printing. Flexo and gravure printing proved unsuitable for producing homogeneous layers due to a Saffman-Taylor instability. Various investigations showed that screen printing using a screen with a very high wet ink film thickness produced the best results. The use of open capillaries in POCT requires the lowest possible contact angle. By applying nanocellulose, it was possible to reduce the contact angle of the cardboard to a suitable value and to change the penetration behavior in that the penetration of an applied liquid first takes place in the nanocellulose. Penetration into the cardboard itself was greatly delayed by the nanocellulose. The functionality of open capillaries could not be achieved in this work due to lack of manufacturing accuracy of additive manufacturing and limited cardboard selection. However, functional closed capillaries could be created using film lamination, allowing fluid transport by capillary forces over a distance of 25 mm without penetration into the cardboard. This shows that the production and use of cardboard-based POCT is theoretically possible.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge