Il existe un réel besoin de développer des matériaux et des technologies avancés pour améliorer l’interface avec le cerveau humain. De tels enregistrements électrophysiologiques sont nécessaires pour des fins diagnostiques ou dans des domaines innovants tels que l’interface homme/machine. Les dispositifs issus de l’électronique organique représentent des alternatives prometteuses grâce à leurs propriétés mécaniques et leur biocompatibilité. L’utilisation de polymères conducteurs ouvre la voie vers une nouvelle interface avec le milieu biologique. Ce travail présente un procédé de fabrication innovant permettant d’intégrer le polymère conducteur PEDOT:PSS sur des électrodes sèches pour une application à l’électroencéphalographie (EEG). L’étape suivante consiste en l’utilisation d’un dispositif actif tel que le transistor organique électrochimique (OECT) afin de profiter de l’amplification locale qu’il permet. Cette dernière est extrêmement importante dans le cas de la neurophysiologie, domaine dans lequel l’amplitude des signaux enregistrés est très basse. En ce sens, l’intégration d’OECTs à des dispositifs d’enregistrement de signaux neuronaux a montré un bien supérieur rapport signal / bruit (SNR) en comparaison à des électrodes conventionnelles. La bioélectronique est un domaine innovant à applications variées. Cette thèse présente la conception et la validation par l’application de dispositifs organiques dans le domaine des neurosciences. D’autres progrès dans les domaines du diagnostic, des biocapteurs, ou de la distribution de médicaments pavent la voie pour de nouvelles applications dans l’agroalimentaire ou encore la qualité de l’eau ou de l’air. / There is a tremendous need for developing advanced materials technologies for interfacing with brain and record neural activity. Such electrophysiological recordings are necessary for diagnostic purposes and brain/machine interfaces. Among the existing technologies, organic electronic devices constitute a promising candidate because of their mechanical flexibility and biocompatibility. The use of conducting polymers, which allow both ionic and electronic transport, allows new modes for interfacing with the biological milieu. This work presents an innovative process to incorporate the conducting polymer poly(3,4-Ethylenedioxythiophene: poly(styrene sulfonate) (PEDOT:PSS) onto electrodes for applications in electroencephalography (EEG). A step beyond conducting polymer electrodes is provided by the Organic Electrochemical Transistor (OECT). The primary advantage of using active devices is the local amplification they provide. This local amplification becomes extremely important in the case of electrophysiological signals, for which the amplitude is very low. The use of the OECT for various electrophysiological measurements is presented, done for clinical purposes like ECG or EEG, for new marketing studies like EOG, and for more fundamental neurological applications, like the recording in vitro of neuronal unitary activity. Bioelectronics is an inspiring field with broad scope. This thesis deals with applications of organic electronic devices in neuroscience. Other applications in diagnostics, biosensing, or drug delivery will offer huge opportunities for food safety, pollution control or even environmental applications.

This thesis focuses on the characterization of PEDOT:DBSA, a new semiconducting polymer for use in bioelectronic devices. It also deals with possibilities of surface treatment in order to enhance its biocompatibility and stability in aqueous environments. For this purpose, the organic polymer films were crosslinked with two crosslinking agents – GOPS and DVS. The ability of these agents to prevent leaching of some fractions of the polymer films in an aqueous environment and the ability to bind polymer molecules to each other as well as to the glass substrate was studied using the delamination test. Subsequently, the effects of these crosslinking agents on the film properties essential for the proper functions of bioelectronics made of these materials, was studied by contact angle measurements and four-point probes respectively. Moreover, several OECTs were prepared using original and crosslinked material as an active layer and were characterized by measuring transconductance and volumetric capacitance. PEDOT:DBSA has been shown to be a suitable material for use in bioelectronics, but its thin layers need to be stabilized in an aqueous environment. The agent DVS appears to be unsuitable for this purpose, mainly due to its insufficient film stabilization and its increased hydrophilicity of the film surface, thus increased tendency to interact with water, resulting in degradation of these thin layers. In contrast, GOPS, despite some reduction in film conductivity, has been able to stabilize the polymer layer over the long term, and thus appears to be a suitable way to stabilize PEDOT:DBSA.

How can the brain be such a good computer? Part of the answer lies in the astonishing number of neurons and synapses that process electrical impulses in parallel. Part of it must be found in the ability of the nervous system to evolve in response to external stimuli and grow, sharpen, and depress synaptic connections. However, we are far from understanding even the basic mechanisms that allow us to think, be aware, recognize patterns, and imagine. The brain can do all this while consuming only around 20 Watts, out-competing any human-made processor in terms of energy-efficiency. This question is of particular interest in a historical era and technological stage where phrases like machine learning and artificial intelligence are more and more widespread, thanks to recent advances produced in the field of computer science. However, brain-inspired computation is today still relying on algorithms that run on traditional silicon-made, digital processors. Instead, the making of brain-like hardware, where the substrate itself can be used for computation and it can dynamically update its electrical pathways, is still challenging. In this work, I tried to employ organic semiconductors that work in electrolytic solutions, called organic mixed ionic-electronic conductors (OMIECs) to build hardware capable of computation. Moreover, by exploiting an electropolymerization technique, I could form conducting connections in response to electrical spikes, in analogy to how synapses evolve when the neuron fires. After demonstrating artificial synapses as a potential building block for neuromorphic chips, I shifted my attention to the implementation of such synapses in fully operational networks. In doing so, I borrowed the mathematical framework of a machine learning approach known as reservoir computing, which allows computation with random (neural) networks. I capitalized my work on demonstrating the possibility of using such networks in-vivo for the recognition and classification of dangerous and healthy heartbeats. This is the first demonstration of machine learning carried out in a biological environment with a biocompatible substrate. The implications of this technology are straightforward: a constant monitoring of biological signals and fluids accompanied by an active recognition of the presence of malign patterns may lead to a timely, targeted and early diagnosis of potentially mortal conditions. Finally, in the attempt to simulate the random neural networks, I faced difficulties in the modeling of the devices with the state-of-the-art approach. Therefore, I tried to explore a new way to describe OMIECs and OMIECs-based devices, starting from thermodynamic axioms. The results of this model shine a light on the mechanism behind the operation of the organic electrochemical transistors, revealing the importance of the entropy of mixing and suggesting new pathways for device optimization for targeted applications.

Additive manufacturing technologies, including inkjet printing, have significantly transformed both research and industry, offering cost-effective and accessible solutions with innovative equipment capabilities. This study focuses on advancing p-type depletion and enhancement-mode poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) through molecular de-doping and rheological measurements, achieving a printing resolution of 30 μm. The versatility of these inks is demonstrated from three distinct perspectives. Firstly, the electrochemical stability of the enhancement-mode behavior opens new possibilities for low-power consumption, stable and sensitive platforms useful for detection of DopamineC and Ascorbic Acid at various concentrations. Secondly, we exemplify the democratization of in-house fabrication through fully printed, all-PEDOT:PSS, transparent, flexible, and bendable paper-based Organic Electrochemical Transistors (OECTs). This showcases the feasibility of employing inkjet printing to create functional electronic devices with ease. Lastly, we explore optimizations that enable deeper personalization by employing multiple material localizations and adjusting the electrical conductivity of OECTs. This engineering approach has resulted in the design of Organic Electrochemical Complementary Amplifiers (OECAs), we incorporated a second formulated enhancement-mode conducting polymer poly(benzimidazobenzophenanthroline) (BBL) as the n-type material to complement the PEDOT:PSS de-doped ink. These developments aim to foster global innovation, representing a significant leap forward in the field of organic electronics and in-house fabrication by complementing this engineering improvement from both fabrication and electrochemistry approaches.

Organic bioelectronics develops electronic devices at the interface with living systems using organic electronic materials. These devices can identify various chemical species and regulate the operation of individual cells, tissues, or organs. A famous organic bioelectronic device is the organic electrochemical transistor (OECT), a highly versatile circuit component that has been used in applications spanning from biosensing to neuromorphic computing. OECTs can be operated in aqueous electrolytes and use organic mixed ionic-electronic conductors (OMIECs) in their channel (and sometimes as gate electrode coating) that can transport electronic and ionic charges, making them ideal for bridging biological systems and silicon-based electronic devices. Electron-transporting (n-type) OMIEC materials have received particular attention because high-performance n-type OECTs can be used to build inverters, sensors, and complementary amplifiers. However, electron transport in an aqueous and ambient environment under the application of electrical fields is a complex phenomenon that requires in situ investigation techniques. Understanding how films operate in such media can allow to construct novel sensors and eliminate the loss processes. This Ph.D. dissertation focuses on the impact of the environment, specifically oxygen, and light, on the performance of n-type OECTs and shows how to use this knowledge to develop OECT-based glucose sensors and photodetectors. Chapter 1 introduces the mixed charge transport phenomenon in conjugated polymers and how to use it in OECT operation. OECT fabrication and various designs are described, setting the ground for the sensors we will show in the following chapters. The experimental procedures used to evaluate the critical figures of merit of the materials and the transistor performance are described in detail. Chapter 2 introduces how OECTs can be used to transduce biochemical binding events. When employing the OECT platform for biochemical sensing, it is essential to differentiate between the faradaic, capacitive, and potentiometric contributions to the sensor response. Understanding the underlying mechanisms is critical for optimizing performance. This chapter explains these different sensing mechanisms with literature examples. Chapter 3 compiles all experimental details relevant to the investigations presented in Chapters 4 and 5. Chapter 4 investigates the working mechanism of a novel n-type OECT-based glucose sensor relying on an enzymatic reaction. This chapter shows the oxygen reaction reactions and the importance of monitoring contact potentials during device operation to understand how detection occurs. The work unveils the role of the oxygen sensitivity of the n-type material on the sensor operation and suggests paths to improve performance. Chapter 5 explores the interactions of light with n-type OMIECs and how to utilize them to build water-compatible phototransistors. The first part of the chapter involves a characterization of the light/matter interplay of an n-type film and a demonstration of how to use it to build a photoelectrochemical transistor. The second part of the chapter expands this work to other n-type materials and assesses their light sensitivity, building a relationship between material property and device performance. Since most detection events lead to a change in the surface of materials, techniques that monitor surface roughness and profile changes in situ can be useful. Chapter 6 describes an atomic force microscopy (AFM) setup that can be used to investigate binding events and electrochemical doping and de-doping dynamics of OMIEC films. This chapter is intended to assist researchers in developing in-operando AFM procedures studying OMIEC films.

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Trilayer polypyrrole microactuators that can operate in air have previously been developed. They consist of two outer layers ofthe electroactive polymer polypyrrole (PPy) and one inner layer of a porous poly(vinylidene flouride) (PVDF) membranecontaining a liquid electrolyte. The two outer layers of PPy are each connected with gold electrodes and separated by the porousPVDF membrane. This microtool is fabricated by bottom-up microfabrication However, porous PVDF layer is not compatible with bottom upmicrofabrication and highly swollen SPE suffers from gold electrode delamination. Hence, in this MSc project/thesis a novelmethod of flexible electrode fabrication with conducting polymers was developed by soft lithography and drop-on-demandprinting. The gold electrodes were replaced by patterned vapor phase polymerized (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT)electrodes due to its high electrical conductivity and versatile process ability. The replacement of the stiff gold electrodes byflexible and stretchable PEDOT allowed high volume change of the material and motions. The PEDOT electrodes werefabricated by patterning the oxidant iron tosylate using microcontact printing and drop-on-demand printing. Moreover, thePVDF membrane has been replaced by a nitrile butadiene rubber/poly(ethylene oxide) semi-interpenetrating polymer network(IPN) to increase ion conductivity and strechability and hence actuator performance.

L’épithélium intestinal est un exemple de tissu qui a évolué pour former une barrière. Cette barrière limite le passage de produits toxiques d’agents pathogènes à partir de la lumière vers les tissus, tout en absorbant les nutriments, électrolytes et l'eau nécessaire à l'hôte. Les jonctions serrées sont des structures qui limitent le passage de la matière à travers l'espace intercellulaire. La capacité de mesurer le transport à travers cette barrière est d'une importance capitale car elle fournit des renseignements sur l’état de celle-ci, révélatrice de certains états pathologiques, puisque la perturbation ou dysfonctionnement des jonctions serrées est souvent due à ou est un indicatif de toxicité ou de maladie. En outre, le degré d'intégrité de la barrière est un indicateur clé de la pertinence d'un modèle in vitro particulier pour une utilisation en toxicologie et screening de médicaments. L'avènement de l'électronique organique a créé une occasion unique pour connecter les mondes de l'électronique et de la biologie, à l'aide des dispositifs tels que le transistor électrochimique organique (OECT), qui fournisse un moyen très sensible pour détecter des courants ioniques. Ces dispositifs ont une sensibilité sans précédent, dans un format qui peut être produit en masse à faible coût.Le but de cette étude était d'intégrer une couche de cellules représentative de la barrière gastro intestinale avec des OECTs, pour créer des dispositifs qui permettent de détecter les perturbations de cette barrière d’une manière rapide et sensible. Cette technique a était démontrée pour être au minimum aussi sensible mais d’une rapidité supérieure que les techniques actuelles sur le marché. / In biological systems, different tissues have evolved to form a barrier. An example is the intestinal epithelium, consisting of a single layer of cells lining the wall of the stomach and colon. It restricts the passage of harmful chemicals or pathogens from the light into the tissue, while selectively absorbing the most nutrients, electrolytes and water are necessary for the host. Tight junctions are structures which limit the passage of the material through the space between the cells. The ability to measure the paracellular and transcellular transport is of vital importance because it provides a wealth of information on the state of the barrier, indicative of certain disease states , since the disruption or malfunction of the structures involved in the transport through the tissue barrier is often caused or is indicative of toxicity or disease. In addition, the degree of integrity of the barrier is a key indicator of the relevance of a particular model in vitro for use in toxicology and drug screening. The advent of organic electronics has created a unique opportunity to connect the worlds of electronics and biology, using devices such as organic electrochemical transistor (OECT), which provides a very sensitive way to detect ionic currents. These devices have unprecedented sensitivity in a format that can be mass produced at low cost.The purpose of this study was to integrate a monolayer of cells representative of the gastro intestinal barrier with OECTs , to create devices that detect disruptions of the barrier in a timely and sensitive manner. This technique was demonstrated to be at least as sensitive, but a higher speed than current techniques on the market

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.

In biological systems, different tissues have evolved to form a barrier. An example is the intestinal epithelium, consisting of a single layer of cells lining the wall of the stomach and colon. It restricts the passage of harmful chemicals or pathogens from the light into the tissue, while selectively absorbing the most nutrients, electrolytes and water are necessary for the host. Tight junctions are structures which limit the passage of the material through the space between the cells. The ability to measure the paracellular and transcellular transport is of vital importance because it provides a wealth of information on the state of the barrier, indicative of certain disease states , since the disruption or malfunction of the structures involved in the transport through the tissue barrier is often caused or is indicative of toxicity or disease. In addition, the degree of integrity of the barrier is a key indicator of the relevance of a particular model in vitro for use in toxicology and drug screening. The advent of organic electronics has created a unique opportunity to connect the worlds of electronics and biology, using devices such as organic electrochemical transistor (OECT), which provides a very sensitive way to detect ionic currents. These devices have unprecedented sensitivity in a format that can be mass produced at low cost.The purpose of this study was to integrate a monolayer of cells representative of the gastro intestinal barrier with OECTs , to create devices that detect disruptions of the barrier in a timely and sensitive manner. This technique was demonstrated to be at least as sensitive, but a higher speed than current techniques on the market