<p>Linköpings Universitet och Acreo AB i Norrköping bedriver ett forskningssamarbete rörande organisk elektrokemisk elektronik och det man kallar papperselektronik. Målet på Acreo är att kunna trycka denna typ av elektronik med snabba trycktekniker så som offset- eller flexotryck. Idag görs de flesta demonstratorer och prototyper, baserade på denna typ av elektrokemisk elektronik, med manuella och subtraktiva mönstringsmetoder. Det skulle vara intressant att hitta fler verktyg och automatiserade tekniker som kan underlätta detta arbete. Målet med detta examensarbete har varit att utvärdera vilken potential bläckstråleteknik respektive screentryck har som tillverkningsmetoder för organiska elektrokemiska elektroniksystem samt att jämföra de båda teknikernas för- och nackdelar. Vad gäller bläckstråletekniken, så ingick även i uppgiften att modifiera en bläckstråleskrivare avsedd för kontor/hemmabruk för att möjliggöra tryckning av de två grundläggande materialen inom organisk elektrokemisk elektronik - den konjugerade polymeren PEDOT och en elektrolyt.</p><p>I denna uppsats rapporteras om hur en procedur för produktion av elektrokemisk elektronik har utvecklats. Världens första elektrokemiska transistor som producerats helt med bläckstråleteknik presenteras tillsammans med fullt fungerande implementeringar i logiska kretsar. Karaktärisering av filmer, komponenter och kretsar som producerats med bläckstråle- och screentrycksteknik har legat till grund för den utvärdering och jämförelse som har gjorts av teknikerna. Resultaten ser lovande ut och kan motivera vidare utveckling av bläckstrålesystem för produktion av prototyper och mindre serier. En kombination av de båda nämnda teknikerna är också ett tänkbart alternativ för småskalig tillverkning.</p> / <p>Linköping University and the research institute Acreo AB in Norrköping are in collaboration conducting research on organic electrochemical electronic devices. Acreo is pushing the development of high-speed reel-to-reel printing of this type of electronics. Today, most demonstrators and prototypes are made using manual, subtractive patterning methods. More tools, simplifying this work, are of interest. The purpose of this thesis work was to evaluate the potential of both inkjet and screen printing as manufacturing tools of electrochemical devices and to conduct a comparative study of these two additive patterning technologies. The work on inkjet printing included the modification of a commercially available desktop inkjet printer in order to print the conjugated polymer PEDOT and an electrolyte solution - these are the two basic components of organic electrochemical devices. For screen printing, existing equipment at Acreo AB was employed for device production.</p><p>In this report the successful development of a simple system and procedure for the inkjet printing of organic electrochemical devices is described. The first all-inkjet printed electrochemical transistor (ECT) and fully functional implementations of these ECTs in printed electrochemical logical circuits are presented.</p><p>The characterization of inkjet and screen printed devices has, along with an evaluation of how suitable the two printing procedures are for prototype production, been the foundation of the comparison of the two printing technologies.</p><p>The results are promising and should encourage further effort to develop a more complete and easily controlled inkjet system for this application. At this stage of development, a combination of the two technologies seems like an efficient approach.</p>

Symmetric and fast (∼5 ms) on-to-off and off-to-on drain current switching characteristics have been obtained in screen printed organic electrochemical transistors (OECTs) including PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid)) as the active transistor channel material. Improvement of the drain current switching characteristics is made possible by including a carbon conductor layer on top of PEDOT:PSS at the drain electrode that is in direct contact with both the channel and the electrolyte of the OECT. This carbon conductor layer suppresses the effects from a reduction front that is generated in these PEDOT:PSS-based OECTs. In the off-state of these devices this reduction front slowly migrate laterally into the PEDOT:PSS drain electrode, which make off-to-on switching slow. The OECT including carbon electrodes was manufactured using only standard printing process steps and may pave the way for fully integrated organic electronic systems that operate at low voltages for applications such as logic circuits, sensors and active matrix addressed displays. / <p>Funding Agencies|Lintec Corporation||</p>

Linköpings Universitet och Acreo AB i Norrköping bedriver ett forskningssamarbete rörande organisk elektrokemisk elektronik och det man kallar papperselektronik. Målet på Acreo är att kunna trycka denna typ av elektronik med snabba trycktekniker så som offset- eller flexotryck. Idag görs de flesta demonstratorer och prototyper, baserade på denna typ av elektrokemisk elektronik, med manuella och subtraktiva mönstringsmetoder. Det skulle vara intressant att hitta fler verktyg och automatiserade tekniker som kan underlätta detta arbete. Målet med detta examensarbete har varit att utvärdera vilken potential bläckstråleteknik respektive screentryck har som tillverkningsmetoder för organiska elektrokemiska elektroniksystem samt att jämföra de båda teknikernas för- och nackdelar. Vad gäller bläckstråletekniken, så ingick även i uppgiften att modifiera en bläckstråleskrivare avsedd för kontor/hemmabruk för att möjliggöra tryckning av de två grundläggande materialen inom organisk elektrokemisk elektronik - den konjugerade polymeren PEDOT och en elektrolyt. I denna uppsats rapporteras om hur en procedur för produktion av elektrokemisk elektronik har utvecklats. Världens första elektrokemiska transistor som producerats helt med bläckstråleteknik presenteras tillsammans med fullt fungerande implementeringar i logiska kretsar. Karaktärisering av filmer, komponenter och kretsar som producerats med bläckstråle- och screentrycksteknik har legat till grund för den utvärdering och jämförelse som har gjorts av teknikerna. Resultaten ser lovande ut och kan motivera vidare utveckling av bläckstrålesystem för produktion av prototyper och mindre serier. En kombination av de båda nämnda teknikerna är också ett tänkbart alternativ för småskalig tillverkning. / Linköping University and the research institute Acreo AB in Norrköping are in collaboration conducting research on organic electrochemical electronic devices. Acreo is pushing the development of high-speed reel-to-reel printing of this type of electronics. Today, most demonstrators and prototypes are made using manual, subtractive patterning methods. More tools, simplifying this work, are of interest. The purpose of this thesis work was to evaluate the potential of both inkjet and screen printing as manufacturing tools of electrochemical devices and to conduct a comparative study of these two additive patterning technologies. The work on inkjet printing included the modification of a commercially available desktop inkjet printer in order to print the conjugated polymer PEDOT and an electrolyte solution - these are the two basic components of organic electrochemical devices. For screen printing, existing equipment at Acreo AB was employed for device production. In this report the successful development of a simple system and procedure for the inkjet printing of organic electrochemical devices is described. The first all-inkjet printed electrochemical transistor (ECT) and fully functional implementations of these ECTs in printed electrochemical logical circuits are presented. The characterization of inkjet and screen printed devices has, along with an evaluation of how suitable the two printing procedures are for prototype production, been the foundation of the comparison of the two printing technologies. The results are promising and should encourage further effort to develop a more complete and easily controlled inkjet system for this application. At this stage of development, a combination of the two technologies seems like an efficient approach.

The emergence of organic electronics - a technology that relies on carbon-based semiconductors to deliver devices with unique properties - represents one of the most dramatic developments of the past two decades. A rapidly emerging new direction in the field involves the interface with biology. The "soft" nature of organics offers better mechanical compatibility with tissue than traditional electronic materials, while their natural compatibility with mechanically flexible substrates suits the non-planar form factors often required for implants. More importantly, their ability to conduct ions in addition to electrons and holes opens up a new communication channel with biology. The coupling of electronics with living tissue holds the key to a variety of important life-enhancing technologies. One example is bioelectronic implants that record neural signals and/or electrically stimulate neurons. These devices offer unique opportunities to understand and treat conditions such as hearing and vision loss, epilepsy, brain degenerative diseases, and spinal cord injury.The engineering aspect of the work includes the development of a photolithographic process to integrate the conducting polymer poly(3,4-ethylenedioxythiophene: poly(styrene sulfonate) (PEDOT:PSS) with parylene C supports to make an active device. The technology is used to fabricate electrocorticography (ECoG) probes, high-speed transistors and wearable biosensors. The experimental work explores the fundamentals of communication at the interface between conducting polymers and the brain. It is shown that conducting polymers outperform conventional metallic electrodes for brain signals recording.Organic electrochemical transistors (OECTs) represent a step beyond conducting polymer electrodes. They consist of a conducting polymer channel in contact with an electrolyte. When a gate electrode excites an ionic current in the electrolyte, ions enter the polymer film and change its conductivity. Since a small amount of ions can effectively "block" the transistor channel, these devices offer significant amplification in ion-to-electron transduction. Using the developed technology a high-speed and high-density OECTs array is presented. The dense architecture of the array improves the resolution of the recording from neural networks and the transistors temporal response are 100 μs, significantly faster than the action potential. The experimental transistor responses are fit and modeled in order to optimize the gain of the transistor. Using the model, an OECT with two orders of magnitude higher normalized transconductance per channel width is fabricated as compared to Silicon-based field effect transistors. Furthermore, the OECTs are integrated to a highly conformable ECoG probe. This is the first time that a transistor is used to record brain activities in vivo. It shows a far superior signal-to-noise-ratio (SNR) compare to electrodes. The high SNR of the OECT recordings enables the observation of activities from the surface of the brain that only a perpetrating probe can record. Finally, the application of OECTs for biosensing is explored. The bulk of the currently available biosensors often require complex liquid handling, and thus suffer from problems associated with leakage and contamination. The use of an organic electrochemical transistor for detection of lactate by integration of a room temperature ionic liquid in a gel-format, as a solid-state electrolyte is demonstrated.

Pas de résumé en français seulement en anglais / The emergence of organic electronics – a technology that relies on carbon-based semiconductors to deliver devices with unique properties – represents one of the most dramatic developments of the past two decades. A rapidly emerging new direction in the field involves the interface with biology. The “soft” nature of organics offers better mechanical compatibility with tissue than traditional electronic materials, while their natural compatibility with mechanically flexible substrates suits the non-planar form factors often required for implants. More importantly, their ability to conduct ions in addition to electrons and holes opens up a new communication channel with biology. The coupling of electronics with living tissue holds the key to a variety of important life-enhancing technologies. One example is bioelectronic implants that record neural signals and/or electrically stimulate neurons. These devices offer unique opportunities to understand and treat conditions such as hearing and vision loss, epilepsy, brain degenerative diseases, and spinal cord injury.The engineering aspect of the work includes the development of a photolithographic process to integrate the conducting polymer poly(3,4-ethylenedioxythiophene: poly(styrene sulfonate) (PEDOT:PSS) with parylene C supports to make an active device. The technology is used to fabricate electrocorticography (ECoG) probes, high-speed transistors and wearable biosensors. The experimental work explores the fundamentals of communication at the interface between conducting polymers and the brain. It is shown that conducting polymers outperform conventional metallic electrodes for brain signals recording.Organic electrochemical transistors (OECTs) represent a step beyond conducting polymer electrodes. They consist of a conducting polymer channel in contact with an electrolyte. When a gate electrode excites an ionic current in the electrolyte, ions enter the polymer film and change its conductivity. Since a small amount of ions can effectively “block” the transistor channel, these devices offer significant amplification in ion-to-electron transduction. Using the developed technology a high-speed and high-density OECTs array is presented. The dense architecture of the array improves the resolution of the recording from neural networks and the transistors temporal response are 100 μs, significantly faster than the action potential. The experimental transistor responses are fit and modeled in order to optimize the gain of the transistor. Using the model, an OECT with two orders of magnitude higher normalized transconductance per channel width is fabricated as compared to Silicon-based field effect transistors. Furthermore, the OECTs are integrated to a highly conformable ECoG probe. This is the first time that a transistor is used to record brain activities in vivo. It shows a far superior signal-to-noise-ratio (SNR) compare to electrodes. The high SNR of the OECT recordings enables the observation of activities from the surface of the brain that only a perpetrating probe can record. Finally, the application of OECTs for biosensing is explored. The bulk of the currently available biosensors often require complex liquid handling, and thus suffer from problems associated with leakage and contamination. The use of an organic electrochemical transistor for detection of lactate by integration of a room temperature ionic liquid in a gel-format, as a solid-state electrolyte is demonstrated.

Grâce à leurs excellentes propriétés mécaniques, électriques et chimiques, les dispositifs organiques électroniques à base de polymères conducteurs peuvent résoudre l’incompatibilité entre les modules électroniques rigides en silicone et les exigences des tissus mous qui constituent l’environnement biologique. Les avancées en matière de semiconducteurs organiques et en microélectronique ont donné naissance à la bioélectronique. Cette discipline emploie des capteurs à des fins diagnostiques, telles que la détection des métabolites ou la mesure d’un potentiel d’action neuronal, et des actionneurs à des fins thérapeutiques, comme l’application locale d’un traitement à l’intérieur même du corps, ou la stimulation cérébrale profonde afin de guérir un trouble neurologique. En bioélectronique, l’utilisation de matériaux organiques, tels que le polymère conducteur poly(3,4-éthylènedioxythiophène) polystyrène sulfonate de sodium (PEDOT:PSS) a permis de développer des composants électroniques biomédicaux de qualité exceptionnelle, comme par exemple le transistor organique électrochimique (OECT), qui ont été testés in vitro et in vivo. Ce manuscrit explique en détail la fabrication, la fonctionnalisation et la caractérisation du OECT à base de PEDOT:PSS. Afin de pouvoir intégrer ce capteur à des systèmes de mesure biomédicaux déjà établis, l’OECT est intégré à des circuits simples, tels qu’un amplificateur de tension ou un pont de Wheatstone. Ces circuits sont mis à l’épreuve de la pratique clinique, dans le cas de mesures électrocardiographiques, ou de détection de métabolites dans des cellules cancéreuses. Cela permet d’apprécier à la fois leur applicabilité, et leurs limites. / Due to their outstanding mechanical, electrical and chemical properties, organic electronic devices based on conducting polymers can bridge the gap between the rigid silicon based read-out electronics and the soft biological environment and will have a huge impact on the medical healthcare sector. The recent advances in the field of organic semiconductors and microelectronics gave rise to a new discipline termed bioelectronics. This discipline deals with sensors for diagnostic purposes, ranging from metabolite detection and DNA recognition all the way to single neuronal firing events, and actuators for therapeutic purposes, through for example active local drug delivery inside the body or deep brain stimulation to cure neurological disorder. The use of organic materials such as the conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in the field of bioelectronics has brought about a variety of outstanding electronic biomedical devices, such as the organic electrochemical transistor (OECT), that have been implemented for both in vitro and in vivo applications. The present manuscript gives a detailed explanation of the fabrication, functionalization and characterization of OECTs based on PEDOT:PSS. To be able to intercept this sensor element with traditional biomedical recording systems, the OECT is implemented into simple circuit layouts such as a voltage amplifier or a Wheatstone bridge. These sensor circuits are then applied to real-life biomedical challenges, such as electrocardiographic recordings or metabolite detection in tumor cell cultures, to demonstrate their applicability as well as their limitations.

L’électrophysiologie est l’étude des signaux électriques et électrochimiques générés par certaines cellules spécifiques tout comme par des organes entiers. Elle donne aux médecins l’opportunité de suivre le fonctionnement d’un seul neurone mais aussi de l’intégralité du cerveau. L’enregistrement de ces activités est essentiel pour le diagnostic de pathologies aussi diverses que les arythmies cardiaques, l’épilepsie ou la dégénération musculaire. Dans cette thèse, nous étudions différents types d’électrodes cutanées à base de matériaux organiques, de leur conception à leur évaluation préclinique. Notre approche est basée sur l’utilisation du polymère conducteur PEDOT :PSS et de gels ioniques, qui réduisent l’impédance de l’interface électrode-peau. De plus, nos électrodes sont conçues avec différents substrats fins et souples, plastiques ou textiles. Ceci appelle de nouvelles techniques de fabrications adaptées à ces substrats et aux matériaux organiques. Les électrodes sont caractérisées puis testées sur des volontaires afin de démontrer leurs excellentes performances par rapport aux électrodes médicales usuelles. L’évaluation de leur capacité à réduire le bruit et de leur stabilité sur plusieurs jours est effectuée sur des signaux venant des activités musculaires, cardiaques et cérébrales. Nous présentons également une électrode microscopique dite « active », basée sur le transistor organique électrochimique. Celui-ci permet d’amplifier et de filtrer in situ le signal. Parce que nos électrodes organiques cutanées possèdent un important potentiel industriel et clinique, nous étudions maintenant leur intégration dans des dispositifs médicaux de pointe. / Electrophysiology is the study of electrical and electrochemical signals generated by specific cells or whole organs. It gives doctors the opportunity to track the physiological behavior of a single neuron, as well as the integral brain. The recording of these activities is essential to diagnose and better understand diseases like cardiac arrhythmias, epilepsy, muscular degeneration and many more. In this thesis, we study different types of cutaneous electrodes based on organic materials, from conception to pre-clinical evaluation. Our approach is based on the usage of PEDOT:PSS conducting polymer and ionic gels in order to reduce impedance at the skin-electrode interface. Moreover, the substrate of our electrodes is made with different materials such as thin and conformable plastics and textiles. Our devices are then flexible, motion resistant and can be integrating into clothes. We developed new fabrication processes, considering the different substrates and organic materials specifics. The electrodes were characterized and then tested on human volunteers to show their excellent performance in comparison to standard medical electrodes. The evaluation of noise reduction capabilities and possibilities to perform long-term recordings were established on signals coming from muscles, heart and brain. Furthermore, we present a hundred micrometer-small “active” electrode, based on the organic electrochemical transistor. It enables in situ amplification and filtering of recorded signals. The wearable organic electrodes developed in this work are of great industrial and clinic interest. Future work will aim to integrate these technologies into state-of-the-art medical devices.

Organické elektronické zariadenia sú vyvíjané ako vhodné riešenia senzorov pre bioelektroniku, a to najmä kvôli dobrej biokompatibilite organických polovodičov v nich použitých. Takzvané biosenzory dokážu premeniť elektrochemické procesy na elektronický signál. Matrica takýchto biosenzorov môže simultánne skenovať množstvo biologických vzoriek, alebo rôznych tkanív v živých systémoch. Aktívnou súčasťou zariadenia je organický elektrochemický tranzistor (OECT). V tejto práci je diskutovaný teoretický rámec fungovania takéhoto zariadenia, jeho elektrická charakterizácia, aplikácia v biosenzoroch na báze buniek, spôsoby výroby a aktuálnym stavom techniky v oblasti organickej elektroniky. Experimentálna časť obsahuje konkrétne výrobné postupy vývoja OECT zariadení, ktoré boli použité v našom laboratóriu. Hlavný dôraz sa kladie na schopnosť vyrobených zariadení detekovať reakciu a monitorovať stimuláciu elektrogenných buniek. Za týmto účelom boli vyvinuté matice mikroelektródových OECT zariadení založených na polovodivom polyméri PEDOT:PSS. Tieto boli vyrobené s využitím bežnými tlačiarenských techník (atramentová tlač a sieťotlač) spolu so štandardnými litografickými postupmi. Najnovšie nami vyvinuté zariadenia dosahujú najväčšieho zosílením signálu, g = 2,5 mS a časovú konštantu t = 0,15 s. Tieto zariadenia sú porovnateľné, často dokonca lepšie ako niektoré iné najmodernejšie a plne litograficky pripravené senzory.

This diploma´s thesis is focused on a study of electrical and dielectric properties of gas sensors based on ionic liquids. Measurements were done on two different types of OECT substrates (0099 and 0160). Three ionic liquids and physiological solution PBS were chosen as electrolytes. Direct current current-voltage characteristic was measured. Switching rations of transistors with this electrolyte were determined by current-voltage characteristic. Alternating resistivity dependence on frequency were measured as well. Better properties showed OECT 0099 substrates.

This diploma thesis is focused on the study of electric and dielectric properties of transistors based on ionic liquids. The measurements were performed on organic electrochemical transistors with a semiconducting channel made of PEDOT:PSS, which were firstly prepared on ITO substrates, later they were printed using 3D print. Ionic liquid NO4 (1-butyl-3-methylimidazolium hydrogensulfate) was used for measuring of the properties. Electrical properties were determined by measuring volt-ampere characteristics, dielectric properties were measured by impedance spectroscopy.