The development of new materials and processes for electronic devices has been driven by the integrated circuit (IC) industry since the dawn of the computer era. After several decades of '"Moore's Law"-type innovation, future miniaturization may be slowed down by materials and processing limitations. By way of comparison, the nascent field of flexible electronics is not driven by the smallest possible circuit dimension, but instead by cost and form-factor where features typical of 1970s CMOS (i.e., channel length - IO μm) will enable flexible electronic technologies such as RFID, e-paper, photovoltaics and health monitoring devices. In this thesis. cyclohexasilane is proposed and used as a key reagent in solution processing of poly-Si and Co-Si thin films with the former used as the active layer in thin film transistors (TFTs) and the latter as the gate metal in metal-oxide-semiconductor (MOS) capacitors. A work function of 4.356 eV was determined for the Co-Si thin films via capacitance-voltage (C-Y) characterization which differs slightly from that extracted from ultraviolet photoemission spectroscopy (UPS) data (i.e., 4.8 eV). Simulation showed the difference between the C-V and UPS-derived data may be attributed to the existence of 8.3 x 10 (exponent 10) cm-2 interface charge density in the oxide-semiconductor junction. Poly-Si TFTs prepared using Si6 H12-based inks maintained the following electrical attributes: field effect mobility of 0.1 cm2V-1s-1; threshold voltage of 66 V; and, an on/off ratio of 1630. A BSIM3 version 3 NFET model was modified through global parametric extraction procedure to match the transfer characteristics of the fabricated poly-Si TFT. It is anticipated that this model can be utilized for future design simulation for solution-processed poly-Si circuits.

Due to their low-temperature processing capability and ionic bonding configuration, amorphous oxide semiconductors (AOS) are well suited for applications within future mechanically flexible electronics. Over the past couple of years, amorphous zinc tin oxide (ZTO) has been proposed as indiumand gallium-free and thus more sustainable alternative to the widely deployed indium gallium zinc oxide (IGZO). The present study specifically focuses on the strain-dependence of elastic and electrical properties of amorphous zinc tin oxide thin-films sputtered at room temperature. Corresponding MESFETs have been compared regarding their operation stability under mechanical bending for radii ranging from 5 to 2 mm. Force-spectroscopic measurements yield a plastic deformation of ZTO as soon as the bending-induced strain exceeds 0.83%. However, the electrical properties of ZTO determined by Hall effect measurements at room temperature are demonstrated to be unaffected by residual compressive and tensile strain up to 1.24 %. Even for the maximum investigated tensile strain of 1.26 %, the MESFETs exhibit a reasonably consistent performance in terms of current on/off ratios between six and seven orders of magnitude, a subthreshold swing around 350 mV/dec and a field-effect mobility as high as 7.5 cm2V−1s−1. Upon gradually subjecting the transistors to higher tensile strain, the channel conductivity steadily improves and consequently, the field-effect mobility increases by nearly 80% while bending the devices around a radius of 2 mm. Further, a reversible threshold voltage shift of about −150 mV with increasing strain is observable. Overall, amorphous ZTO provides reasonably stable electrical properties and device performance for bending-induced tensile strain up to at least 1.26% and thus represent a promising material of choice considering novel bendable and transparent electronics.

<p>In the last 30 years, the possibility of using polymeric thin film transistors (PTFTs) in flexible display, sensors, radio-frequency identification tag and the potential of using printing or low-cost reel-to-reel fabrication techniques has stimulated much research and technology development in these devices. However, the utilization of PTFTs needs better understanding of the organic semiconductor material’s properties and their physical and chemical mechanisms. In addition, the PTFTs show poor stability compared to the crystalline transistors. The PTFTs can have significant variations of threshold voltage, mobility, on/off ratio even when deposited using the same conditions on the same substrate. Therefore, better understanding of the PTFTs’ physical and chemical properties and the improvement of the characterization techniques are needed.</p> <p>The design and fabrication of the novel polymeric semiconductor, diketopyrrolopyrrole β-unsubstituted quaterthiophene (DKPP-βT) based bottom-gated top-contact PTFT and microfluidics PTFT are introduced in this thesis. The microfluidic PTFT consists of polydimethylsiloxane (PDMS) microchannel which guides liquids flowing over the top of the semiconductor channel.</p> <p>From consecutive electrical measurements, it was found that the threshold voltage (V_T) follows a logarithmic law function of the time. Illuminating the PTFTs results in shifts of the initial value of the threshold voltage linearly towards more positive value. The mobility is unaffected by time or by illumination. However, the off current increased proportionally with light. Also, the contact resistance extracted by the parameter compensated transmission line model (TLM) method is ohmic and gate bias independent for high gate biases.</p> <p>The novel microfluidic PTFT enables the study of the sensing property of the DKPP-βT PTFT of liquid analytes. The threshold voltage evolution in the deionized (DI) water measurements also follows logarithmic function of the time with a slightly steeper slope than in air. The mobility only slightly decreases initially on exposure to DI water. The off current in DI water measurements decrease compared with air measurements. In acid solution measurements, the threshold voltage remains stable and the mobility slightly increased, compared with measurements in water. Additionally, the subthreshold slope and off current in both acid solution and salt water measurements show similar results to the DI water measurements. While the base solution damages the device immediately. The stable performance of DKPP-βT PTFTs with DI water and low-concentration salt water in the microchannel makes it a promising biosensor.</p> / Master of Applied Science (MASc)

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.

Indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) are investigated for thin-film transistor (TFT) applications. Negative bias illumination stress (NBIS) is employed for electrical stability assessment. Unpassivated IGZO and ZTO TFTs suffer from severe NBIS instabilities. Zinc-tin-silicon oxide is found to be an effective passivation layer for IGZO and ZTO TFTs, significantly improving the NBIS stability. NBIS instabilities in unpassivated TFTs are attributed to an NBIS-induced desorption of chemisorbed oxygen from the channel layer top surface, exposing surface oxygen vacancies. A ZTSO layer protects the channel layer top surface from adsorbed gas interactions and also appears to reduce the density of oxygen vacancies. The best device architectures investigated with respect to TFT electrical performance are found to be staggered with aluminum electrodes for unpassivated TFTs and coplanar with ITO electrodes for ZTSO-passivated TFTs. Annealing in wet-O₂ is not found to be effective for improving the performance of IGZO or ZTO TFTs or for reducing the post-deposition annealing temperature. / Graduation date: 2012

The work carried out in this thesis systematically investigates the correlation between microstructures and electronic properties of organic semiconductors. The major directions that were pursued in this thesis are: (i) studies on structure-property relationship by rational design and synthesis of monodisperse oligomers with varying chain-lengths (ii) role of electronic properties and aggregation (microstructures) in governing singlet fission (SF). In the first part of the thesis, the optical, structural and charge transport properties of Diketopyrrolopyrrole (DPP)-based oligomers, as a function of the chain length, has been discussed. The energy bands became wider with an increase in chain length and a gain in backbone electron affinity was observed, with an offset in microstructural order. With an increase in chain length, the tendency to form intramolecular aggregates increased as compared to intermolecular aggregates due to the onset of backbone conformational defects and chain folding. An insight into the solid-state packing and microstructural order has been obtained by steady-state and transient spectroscopy, grazing incidence small angle x-ray scattering (GISAXS), atomic force microscopy (AFM) and transmission electron microscopy (TEM) studies. The charge-carrier mobilities varied in accordance with the degree of microstructural order as: dimer > trimer > pentamer. A library of DPP-DPP based trimers was also generated by modifying the donor chromophore (phenyl, thiophene and selenophene) in the oligomer backbone. Highest n-channel mobility of ~0.2 cm2V-1s-1 was obtained which validated that: (a) the effect of solid-state packing predominates the effect of backbone electronic structure on charge carrier mobility. Although oligomers possess lesser backbone defects than polymers in general, their charge carrier mobilities were not comparable to that of 2DPP-OD-TEG polymer, which forms highly oriented and isotropic edge-on crystallites/microstructures in the thin film, shows high n-channel mobility of 3 cm2V-1s-1 and band-like transport ;(b) although delocalized electronic states are achieved at greater chain lengths, the degree of solid-state microstructural order drastically reduces which leads to lower charge carrier mobilities; (c) conformational collapse resulted in lower electron mobilities and an increase in ambipolarity. The later part of the thesis debates on the relative contribution of electronic structure and aggregation (microstructures) in governing singlet fission (SF). Motivated by the recent SF model in carotenoid aggregates, a DPP-DPP based oligomer was synthesized by incorporating a vinylene bridge to imbue “polyene” character in the chromophore. Transient Spectroscopy (TA) measurements were carried out to monitor the formation of triplet states in the oligomer and to probe the occurrence of singlet fission. Although the oligomer exhibits “polyene” character like a typical “carotenoid aggregate”, it did not show singlet fission because of the additional stabilization of the singlet (S1) state which reduces the ∆EST. This study rationalized the importance of judicious control of band structures as well as microstructures to observe the SF phenomenon in this category of chromophores. The novel synthetic protocol provides the scope to tailor DPP-DPP based materials with desired effective conjugation lengths and side chains and can foreshow great prospects for future generation of organic electronics.

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.

Organic electronic devices such as organic field effect transistors (OFETs), light- emitting diodes (OLEDs), resistive memory elements or organic solar cells have attracted an increasing attention in recent years due to the vision of a low-cost and large-scale production of printable electronics. Many papers published during the last decade focused on the intrinsic properties of organic conductors, semiconductors and dielectric materials. Since most of the devices consist of multilayer structures the mutual influence of the processes that take place in the particular layers are important for the functionality of the whole device. This work is aimed to contribute to the characterization and understanding of the mutual interactions of individual layers in the multilayer structures of organic devices. The main achievements of this work can be listed as: (i) Optimization of the thermal stability and dielectric properties of cyanoethylated polyvinylalcohol (CEPVA) high-k dielectric by the crosslinking reaction with the low molecular weight materials or mixing with a high Tg polymer. (ii) Finding possible phenomena in the CEPVA polymer dielectric that influence the charge carrier transport in the OFET active channel made of bis(triisopropylsilylethynyl) pentacene organic semiconductor, using a...

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

Electrostatic Discharge (ESD) is a significant hazard to electronic components and systems. Based on a specific processing technology, a given circuit application requires a customized ESD consideration that includes the devices’ operating voltage, leakage current, breakdown constraints, and footprint. As new technology nodes mature every 3-5 years, design of effective ESD protection solutions has become more and more challenging due to the narrowed design window, elevated electric field and current density, as well as new failure mechanisms that are not well understood. The endeavor of this research is to develop novel, effective and robust ESD protection solutions for both emerging technologies and modern complementary metal–oxide–semiconductor (CMOS) technologies. The Si nanowire field-effect transistors are projected by the International Technology Roadmap for Semiconductors as promising next-generation CMOS devices due to their superior DC and RF performances, as well as ease of fabrication in existing Silicon processing. Aiming at proposing ESD protection solutions for nanowire based circuits, the dimension parameters, fabrication process, and layout dependency of such devices under Human Body Mode (HBM) ESD stresses are studied experimentally in company with failure analysis revealing the failure mechanism induced by ESD. The findings, including design methodologies, failure mechanism, and technology comparisons should provide practical knowhow of the development of ESD protection schemes for the nanowire based integrated circuits. Organic thin-film transistors (OTFTs) are the basic elements for the emerging flexible, printable, large-area, and low-cost organic electronic circuits. Although there are plentiful studies focusing on the DC stress induced reliability degradation, the operation mechanism of OTFTs iv subject to ESD is not yet available in the literature and are urgently needed before the organic technology can be pushed into consumer market. In this work, the ESD operation mechanism of OTFT depending on gate biasing condition and dimension parameters are investigated by extensive characterization and thorough evaluation. The device degradation evolution and failure mechanism under ESD are also investigated by specially designed experiments. In addition to the exploration of ESD protection solutions in emerging technologies, efforts have also been placed in the design and analysis of a major ESD protection device, diodetriggered-silicon-controlled-rectifier (DTSCR), in modern CMOS technology (90nm bulk). On the one hand, a new type DTSCR having bi-directional conduction capability, optimized design window, high HBM robustness and low parasitic capacitance are developed utilizing the combination of a bi-directional silicon-controlled-rectifier and bi-directional diode strings. On the other hand, the HBM and Charged Device Mode (CDM) ESD robustness of DTSCRs using four typical layout topologies are compared and analyzed in terms of trigger voltage, holding voltage, failure current density, turn-on time, and overshoot voltage. The advantages and drawbacks of each layout are summarized and those offering the best overall performance are suggested at the end