Submitted by Gabriel Leonardo Nogueira (gabrielnogueira5@hotmail.com) on 2016-11-02T14:46:19Z No. of bitstreams: 1 Dissertação Gabriel FINAL corrigida.pdf: 3857264 bytes, checksum: 37885bf252f0c527d86237d787b4fe47 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-11-10T12:25:58Z (GMT) No. of bitstreams: 1 nogueira_gl_me_prud.pdf: 3857264 bytes, checksum: 37885bf252f0c527d86237d787b4fe47 (MD5) / Made available in DSpace on 2016-11-10T12:25:58Z (GMT). No. of bitstreams: 1 nogueira_gl_me_prud.pdf: 3857264 bytes, checksum: 37885bf252f0c527d86237d787b4fe47 (MD5) Previous issue date: 2016-08-26 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O transistor orgânico de efeito de campo com arquitetura vertical (VOFET) possibilita contornar as principais limitações de um transistor orgânico de efeito de campo (OFET) convencional. Nesta estrutura, as camadas são empilhadas verticalmente, de modo que os eletrodos de fonte e dreno são separados pela camada semicondutora e o comprimento do canal definido pela espessura do filme semicondutor. Para o VOFET proposto, utilizou-se Al e Al2O3 (obtido por anodização) como eletrodo e dielétrico de gate, respectivamente. O filme semicondutor foi obtido pela deposição por spincoating de P3HT dissolvido em clorofórmio. Os eletrodos de fonte e dreno foram obtidos por evaporação térmica a vácuo. Ao utilizar Al e Au como fonte e dreno, respectivamente, foi possível estudar os dispositivos de dois terminais que compõe o VOFET. Com base nesses dispositivos, importantes parâmetros da estrutura vertical foram determinados, como capacitância do dielétrico (~265 nF/cm2), densidade de portadores e mobilidade do P3HT (NA = 9,2 x 1016 cm-3 e μ = 1,5x10-4 cm2V-1s-1). Para utilizar Sn como eletrodo de fonte, o filme foi avaliado por meio de medidas de resistência e capacitância, aliadas à analise morfológica por AFM. Observa-se que a adição de uma camada de PMMA sobre o Al2O3 melhora o desempenho do VOFET. Para o VOFET formado por Al2O3/PMMA (20 nm/14 nm), com Sn e Al como fonte e dreno, foram calculados os valores de densidade de corrente (Jeff = 7x10-3 mA/cm2), voltagem e campo limiar (VTH = -8V e ELIMIAR = 330 MV/m). Com isso, foi obtido um VOFET utilizando filme de Sn evaporado como eletrodo de fonte perfurado. / A way of circumvent the limitations of conventional organic field-effect transistor (OFET), is by using the vertical organic field-effect transistor (VOFET). In this structure, with layers stacked vertically, the semiconductor is sandwiched between source and drain electrodes, where the channel length is determined by the thickness of the semiconductor film. In this study, we report a VOFET with Al and Al2O3 (obtained by anodization) as electrode and dielectric of gate, respectively. The semiconductor film was obtained by spin-coating of the P3HT in chloroform. We obtained the source and drain electrodes by vacuum thermal evaporation. The use of Al and Au as source and drain, respectively, enabled the investigation of the two devices contained in the VOFET (MIM capacitor, Schottky diode and MIS capacitor). Important parameters were determinate, as dielectric capacitance (~265 nF/cm2), charrier density and mobility of P3HT (NA = 9,2 x 1016 cm-3 e μ = 1,5x10-4 cm2V-1s-1), etc. To use Sn as source electrode, the film (by evaporation) was investigated by measurements of resistance and capacitance, combined with morphological analysis by AFM. We observed that the addiction of PMMA layer on Al2O3 improves the performance of VOFET. For VOFET obtained by using Al2O3/PMMA (20 nm/14 nm) as dielectric layer, with Sn and Al as source and drain, respectively, were calculate the values of current density (Jeff = 7x10-3 mA/cm2), threshold voltage and electric field (VTH = -8V e ETH = 330 MV/m). Thereat, we obtained a VOFET by evaporation of a thin film of Sn as perforated source electrode. / FAPESP: 2013/26973-5

Diese Arbeit stellt eine eingehende Studie des sogenannten Vertikalen Organischen Feld-Effekt-Transistors (VOFET) dar, einer neuen Transistor-Geometrie, welche dem stetig wachsenden Bereich der organischen Elektronik entspringt. Dieses neuartige Bauteil hat bereits bewiesen, dass es in der Lage ist, eine der fundamentalen Einschränkungen herkömmlicher organischer Feld-Effekt-Transistoren (OFETs) zu überwinden: Die für Schaltfrequenz und An-Strom wichtige Kanallänge des Transistors kann im VOFET stark reduziert werden, ohne dass teure und komplexe Strukturierungsmethoden genutzt werden müssen. Das genaue Funktionsprinzip des VOFET ist bisher jedoch weitgehend unerforscht. Durch den Vergleich von experimentellen Daten mit Simulationsdaten des erwarteten Bauteil-Verhaltens wird hier ein erstes, grundlegendes Verständnis des VOFETs erarbeitet. Die so gewonnenen Erkenntnisse werden im Folgenden genutzt, um bestimmte Parameter des VOFETs kontrolliert zu manipulieren. So wird beispielsweise gezeigt, dass die Morphologie des organischen Halbleiters, und damit seine Abscheidungsparameter, sowohl für die VOFET-Herstellung als auch für den Ladungsträgertransport im fertigen Bauteil eine wichtige Rolle spielen. Weiterhin wird gezeigt, dass der VOFET, genau wie der konventionelle OFET, durch das Einbringen von Kontaktdotierung deutlich verbessert werden kann. Mit Hilfe dieser Ergebnisse kann gezeigt werden, dass das Funktionsprinzip des VOFETs mit dem eines konventionellen OFETs nahezu identisch ist, wenn man von geringen Abweichungen aufgrund der unterschiedlichen Geometrien absieht. Basierend auf dieser Erkenntnis wird schließlich ein VOFET präsentiert, welcher im Inversionsmodus betrieben werden kann und so die Lücke zur konventionellen MOSFET-Technologie schließt. Dieser Inversions-VOFET stellt folglich einen vielversprechenden Ansatz für leistungsfähige organische Transistoren dar, welche als Grundbausteine für komplexe Elektronikanwendungen auf flexiblen Substraten genutzt werden können. / This work represents a comprehensive study of the so-called vertical organic field-effect transistor (VOFET), a novel transistor geometry originating from the fast-growing field of organic electronics. This device has already demonstrated its potential to overcome one of the fundamental limitations met in conventional organic transistor architectures (OFETs): In the VOFET, it is possible to reduce the channel length and thus increase On-state current and switching frequency without using expensive and complex structuring methods. Yet the VOFET's operational principles are presently not understood in full detail. By simulating the expected device behaviour and correlating it with experimental findings, a basic understanding of the charge transport in VOFETs is established and this knowledge is subsequently applied in order to manipulate certain parameters and materials in the VOFET. In particular, it is found that the morphology, and thus the deposition parameters, of the organic semiconductor play an important role, both for a successful VOFET fabrication and for the charge transport in the finished device. Furthermore, it is shown that VOFETs, just like their conventional counterparts, are greatly improved by the application of contact doping. This result, in turn, is used to demonstrate that the VOFET essentially works in almost exactly the same way as a conventional OFET, with only minor changes due to the altered contact arrangement. Working from this realisation, a vertical organic transistor is developed which operates in the inversion regime, thus closing the gap to conventional MOSFET technology and providing a truly promising candidate for high-performance organic transistors as the building blocks for advanced, flexible electronics applications.

Diese Arbeit stellt eine eingehende Studie des sogenannten Vertikalen Organischen Feld-Effekt-Transistors (VOFET) dar, einer neuen Transistor-Geometrie, welche dem stetig wachsenden Bereich der organischen Elektronik entspringt. Dieses neuartige Bauteil hat bereits bewiesen, dass es in der Lage ist, eine der fundamentalen Einschränkungen herkömmlicher organischer Feld-Effekt-Transistoren (OFETs) zu überwinden: Die für Schaltfrequenz und An-Strom wichtige Kanallänge des Transistors kann im VOFET stark reduziert werden, ohne dass teure und komplexe Strukturierungsmethoden genutzt werden müssen. Das genaue Funktionsprinzip des VOFET ist bisher jedoch weitgehend unerforscht. Durch den Vergleich von experimentellen Daten mit Simulationsdaten des erwarteten Bauteil-Verhaltens wird hier ein erstes, grundlegendes Verständnis des VOFETs erarbeitet. Die so gewonnenen Erkenntnisse werden im Folgenden genutzt, um bestimmte Parameter des VOFETs kontrolliert zu manipulieren. So wird beispielsweise gezeigt, dass die Morphologie des organischen Halbleiters, und damit seine Abscheidungsparameter, sowohl für die VOFET-Herstellung als auch für den Ladungsträgertransport im fertigen Bauteil eine wichtige Rolle spielen. Weiterhin wird gezeigt, dass der VOFET, genau wie der konventionelle OFET, durch das Einbringen von Kontaktdotierung deutlich verbessert werden kann. Mit Hilfe dieser Ergebnisse kann gezeigt werden, dass das Funktionsprinzip des VOFETs mit dem eines konventionellen OFETs nahezu identisch ist, wenn man von geringen Abweichungen aufgrund der unterschiedlichen Geometrien absieht. Basierend auf dieser Erkenntnis wird schließlich ein VOFET präsentiert, welcher im Inversionsmodus betrieben werden kann und so die Lücke zur konventionellen MOSFET-Technologie schließt. Dieser Inversions-VOFET stellt folglich einen vielversprechenden Ansatz für leistungsfähige organische Transistoren dar, welche als Grundbausteine für komplexe Elektronikanwendungen auf flexiblen Substraten genutzt werden können.:Zusammenfassung 5 Abstract 6 Publications 13 Introduction 17 Basic Principles of Organic Semiconductors and Related Devices 23 1. The Physics of Organic Semiconductors 25 1.1. Electronic and structural properties of organic semiconductors 28 1.2. Charge carrier transport 34 1.3. Doping of organic semiconductors 43 2. Organic field-effect transistors 47 2.1. Operational principle 50 2.2. Functional interfaces in OFETs 55 2.3. Contact resistance and short-channel effects in OFETs 60 2.4. Applications of OFETs and related devices 65 3. Vertical organic transistors 77 3.1. Organic permeable-base transistors (OPBTs) and organic static induction transistors (OSITs) 81 3.2. Organic Schottky barrier transistors (OSBTs) 85 3.3. Vertical organic field-effect transistors (VOFETs) 90 Study of the Vertical Organic Field-Effect Transistor 97 4. Methods and Materials 99 4.1. Materials 101 4.2. Sample preparation 104 4.3. Sample characterisation 110 5. Material Optimisation for VOFETs 121 5.1. Variation of the source insulator 123 5.2. Effects of the pentacene morphology 133 5.3. Summary 137 6. Charge Transport in the VOFET 139 6.1. Simulating current flow in the VOFET 141 6.2. The vertical channel 154 6.3. Charge transport in pentacene 161 6.4. Effects of mobility and layer thickness in pentacene VOFETs 167 6.5. Summary 175 7. Doping Concepts for VOFETs 177 7.1. Doping of the bulk regions 179 7.2. Selective contact doping 183 7.3.Impact on the understanding of VOFET operation 194 7.4. Summary 198 8. Vertical Organic Inversion Transistors 201 8.1. Discussion of suitable material systems 204 8.2. Realising inversion VOFETs 207 8.3. Summary 212 9. Conclusion and Outlook 215 9.1. Conclusion 217 9.2. Outlook 219 Appendix 221 A. XRD spectra of pentacene films 223 B. Additional simulation data 227 Bibliography 229 Addresses 257 Important Symbols, Constants and Abbreviations 263 List of Figures 271 Acknowledgements 283 / This work represents a comprehensive study of the so-called vertical organic field-effect transistor (VOFET), a novel transistor geometry originating from the fast-growing field of organic electronics. This device has already demonstrated its potential to overcome one of the fundamental limitations met in conventional organic transistor architectures (OFETs): In the VOFET, it is possible to reduce the channel length and thus increase On-state current and switching frequency without using expensive and complex structuring methods. Yet the VOFET's operational principles are presently not understood in full detail. By simulating the expected device behaviour and correlating it with experimental findings, a basic understanding of the charge transport in VOFETs is established and this knowledge is subsequently applied in order to manipulate certain parameters and materials in the VOFET. In particular, it is found that the morphology, and thus the deposition parameters, of the organic semiconductor play an important role, both for a successful VOFET fabrication and for the charge transport in the finished device. Furthermore, it is shown that VOFETs, just like their conventional counterparts, are greatly improved by the application of contact doping. This result, in turn, is used to demonstrate that the VOFET essentially works in almost exactly the same way as a conventional OFET, with only minor changes due to the altered contact arrangement. Working from this realisation, a vertical organic transistor is developed which operates in the inversion regime, thus closing the gap to conventional MOSFET technology and providing a truly promising candidate for high-performance organic transistors as the building blocks for advanced, flexible electronics applications.:Zusammenfassung 5 Abstract 6 Publications 13 Introduction 17 Basic Principles of Organic Semiconductors and Related Devices 23 1. The Physics of Organic Semiconductors 25 1.1. Electronic and structural properties of organic semiconductors 28 1.2. Charge carrier transport 34 1.3. Doping of organic semiconductors 43 2. Organic field-effect transistors 47 2.1. Operational principle 50 2.2. Functional interfaces in OFETs 55 2.3. Contact resistance and short-channel effects in OFETs 60 2.4. Applications of OFETs and related devices 65 3. Vertical organic transistors 77 3.1. Organic permeable-base transistors (OPBTs) and organic static induction transistors (OSITs) 81 3.2. Organic Schottky barrier transistors (OSBTs) 85 3.3. Vertical organic field-effect transistors (VOFETs) 90 Study of the Vertical Organic Field-Effect Transistor 97 4. Methods and Materials 99 4.1. Materials 101 4.2. Sample preparation 104 4.3. Sample characterisation 110 5. Material Optimisation for VOFETs 121 5.1. Variation of the source insulator 123 5.2. Effects of the pentacene morphology 133 5.3. Summary 137 6. Charge Transport in the VOFET 139 6.1. Simulating current flow in the VOFET 141 6.2. The vertical channel 154 6.3. Charge transport in pentacene 161 6.4. Effects of mobility and layer thickness in pentacene VOFETs 167 6.5. Summary 175 7. Doping Concepts for VOFETs 177 7.1. Doping of the bulk regions 179 7.2. Selective contact doping 183 7.3.Impact on the understanding of VOFET operation 194 7.4. Summary 198 8. Vertical Organic Inversion Transistors 201 8.1. Discussion of suitable material systems 204 8.2. Realising inversion VOFETs 207 8.3. Summary 212 9. Conclusion and Outlook 215 9.1. Conclusion 217 9.2. Outlook 219 Appendix 221 A. XRD spectra of pentacene films 223 B. Additional simulation data 227 Bibliography 229 Addresses 257 Important Symbols, Constants and Abbreviations 263 List of Figures 271 Acknowledgements 283

The following dissertation addresses a novel low cost process developed to fabricate a Vertical Organic Field Effect Transistor (VOFET). The solution processable VOFET is designed, fabricated and tested in the context of bioengineering domains. The scope of distinct biomedical applications has also been explored. Organic thin-film transistors are gathering industrial attention as a potential candidate for future electronics analogous to silicon technology. Low fabrication cost, structural miniaturization and low operational voltage are the challenges for fabricating an Organic Field Effect Transistor (OFET). To create these devices, OFETs require new design paradigms and wet processing routes. However, conventional lateral OFET geometry cannot satisfy these demands because of process complexities and the high cost to achieve sub-micron channel length. Despite these barriers, solvent sensitivity towards organic semiconductors, electrode patterning and masking make this process more challenging than are associated with current technologies. Therefore, the need for production of a low cost high efficiency OFET is of high importance. The soluble organic semiconductor exhibits promising device properties. The growing demand of organic electronics poses great difficulty in adapting standard photolithography patterning for fabrication. The main issue is incompatibility in handling organic materials. To circumvent these challenges, a novel fabrication process has been developed to build OFETs in vertical geometry. The novelty of this process allows for creation of sub-micron channel devices at very low cost. Solution processed VOFET devices are fabricated using a 13,6-N-sulfinylacetamidopentacene (NSFAAP) precursor. Low cost fabrication techniques such as spin coating and drop casting are employed for achieving submicron channel length. Nanoscale devices, i.e. channel lengths, L=265nm, 300nm and 535nm, are respectively fabricated using the spin coating technique. Output characteristics are recorded at an operational voltage of 1volt. Short channel effects dominate the device performance, resulting in a linearity effect in I-V characteristics. Strategies, such as perforated source electrode design and drop casting techniques, are evolved and employed to minimize the short channel effects. Space Charge Limited Current (SCLC) effects, better known as short channel effects, are observed during I-V characterizations at high longitudinal fields. The drop casting technique is used over Patterned Electrode (PE) for reducing these SCLC effects. Thick channel devices, i.e. L=2µm, are fabricated to minimize the SCLC effects. Low cost polyimide 3M kapton tape is used as masking material in between the stacked layers. Time-temperature balance is optimized during the precursor to pentacene growth process. Metrological characterizations such as TEM, SEM, AFM, Raman Spectroscopy and X-RD are performed to confirm the precursor to pentacene conversion. AFM scanning illustrates dendritic pentacene molecular growth at 170°C annealing. Consequently, the conversion temperature is optimized around 200°C. In life sciences, there is always striving for translational technology development that can mimic, integrate and manipulate the biological system. Electrical signals enhance the capabilities of electronics to interact and understand the signaling pathways in a biological system. Keeping this in view, the potential applications into biomedical areas, such as flexible sensors and biomedical imagers, are proposed. VOFET has been proposed as a mainstay for flexible cardiac sensors and as imagers. OFET sensors could be designed to cover highly stretchy and arbitrary cardiac tissue. Sensor web integration with pacemakers and Implantable Cardioverter Defibrillator (ICD) device systems has been proposed. The OFET imaging sensor holds potential for early detection of cancer by detecting nuclear level changes in breast cancer images. Nuclear pleomorphic (shape and size distortion of cancerous nuclei) feature detection and analysis could be a step forward in the direction of digital pathology. The conventional analysis approach is time-consuming and error prone as it depends on visual inspection by pathologists. The proposed approach is parallel in nature and supports the existing method of cancer detection.