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.

We report on the detailed electrical investigation of all-inkjet-printed thin-film transistor (TFT) arrays focusing on TFT failures and their origins. The TFT arrays were manufactured on flexible polymer substrates in ambient condition without the need for cleanroom environment or inert atmosphere and at a maximum temperature of 150 °C. Alternative manufacturing processes for electronic devices such as inkjet printing suffer from lower accuracy compared to traditional microelectronic manufacturing methods. Furthermore, usually printing methods do not allow the manufacturing of electronic devices with high yield (high number of functional devices). In general, the manufacturing yield is much lower compared to the established conventional manufacturing methods based on lithography. Thus, the focus of this contribution is set on a comprehensive analysis of defective TFTs printed by inkjet technology. Based on root cause analysis, we present the defects by developing failure categories and discuss the reasons for the defects. This procedure identifies failure origins and allows the optimization of the manufacturing resulting finally to a yield improvement.

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

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.

We report on the detailed electrical investigation of all-inkjet-printed thin-film transistor (TFT) arrays focusing on TFT failures and their origins. The TFT arrays were manufactured on flexible polymer substrates in ambient condition without the need for cleanroom environment or inert atmosphere and at a maximum temperature of 150 °C. Alternative manufacturing processes for electronic devices such as inkjet printing suffer from lower accuracy compared to traditional microelectronic manufacturing methods. Furthermore, usually printing methods do not allow the manufacturing of electronic devices with high yield (high number of functional devices). In general, the manufacturing yield is much lower compared to the established conventional manufacturing methods based on lithography. Thus, the focus of this contribution is set on a comprehensive analysis of defective TFTs printed by inkjet technology. Based on root cause analysis, we present the defects by developing failure categories and discuss the reasons for the defects. This procedure identifies failure origins and allows the optimization of the manufacturing resulting finally to a yield improvement.

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.