Organic solar cells have been showing promise as a way of producing renewableenergy with the help of light, flexible, and production effective materials.The efficiencies and lifetimes reached in organic solar cells have steadily beenincreasing over the years as more research in the field is being conducted.One way of increasing the efficiency in organic solar cell devices is introducingan interlayer between the photoactive material and the anode, referred toas the ’hole transport layer’. Most commonly used as a hole transport layer isthe material PEDOT:PSS, which offers desired properties such as transparency,simple processing and good ohmic contact between anode and photoactive material.PEDOT:PSS is also known to be a degradation site in organic solar cells,as it will corrode the electrode in the presence of water.This project has consisted of investigating PEDOT:PSS along with two othercandidates that may one day come to replace PEDOT:PSS as the most commonlyused material, molybdenum trioxide (MoO3) and phosphomolybdic acid(PMA). The aim was to investigate how the different materials energy bandstructure would be affected upon exposure to sunlight, air and annealing, byobserving the work function under different conditions.

De nos jours, efficacité et précision des diagnostics médicaux sont des éléments essentiels pour la prévention en termes de santé et permettre une prise en charge rapide des maladies des patients. Les récentes innovations technologiques, particulièrement dans les domaines de la microélectronique et des sciences des matériaux ont permis le développement de nouvelles plateformes personnalisées de diagnostics portatifs. Les matériaux électroniques organiques qui ont déjà par le passé démontré leur potentiel en étant intégrés dans des produits de grande consommation tels que les écrans de smartphones ou encore les cellules solaires montrent un fort potentiel pour une intégration dans des dispositifs biomédicaux. En effet, de par leurs natures et leurs propriétés physiques et chimiques, ils peuvent être à la fois en contact avec les milieux biologiques et constituer l’interface entre les éléments biologiques à l’étude, et les dispositifs électroniques. L’objectif de mes travaux de thèse et d’étudier et évaluer les performances des matériaux organiques électroniques intégrés dans des dispositifs biomédicaux en étudiant leurs interactions avec des milieux biologiques et par l’utilisation et l’optimisation de ces dispositifs permettre la détection de métabolites tel que le glucose ou lactate par exemple. Pendant ma thèse, j’ai notamment créé une plateforme de diagnostics combinant à la fois microfluidique et électronique organique permettant la multi détection de métabolites présents dans des fluides corporels humains, j’ai également conçu des capteurs intégrant des transistors organiques au sein des circuits électroniques classiques afin de détecter la présence des cellules tumorales. D’autres applications biologiques ont également été envisagées telles que la détection d’acides nucléiques par l’utilisation d’une approche simple de biofonctionnalisation. Bien que l’objectif ma thèse était de de créer des capteurs biomédicaux en utilisant une approche in vitro, il pourrait être également possible d’intégrer ces dispositifs « in vivo » ou encore dans des e-textiles. / Rapid and early diagnosis of disease plays a major role in preventative healthcare. Undoubtedly, technological evolutions, particularly in microelectronics and materials science, have made the hitherto utopian scenario of portable, point-of-care personalized diagnostics a reality. Organic electronic materials, having already demonstrated a significant technological maturity with the development of high tech products such as displays for smartphones or portable solar cells, have emerged as especially promising candidates for biomedical applications. Their soft and fuzzy nature allows for an almost seamless interface with the biological milieu rendering these materials ideally capable of bridging the gap between electronics and biology. The aim of this thesis is to explore and validate the capabilities of organic electronic materials and devices in real-world biological sensing applications focusing on metabolite sensing, by combining both the right materials and device engineering. We show proof-of-concept studies including microfluidic integrated organic electronic platforms for multiple metabolite detection in bodily fluids, as well as more complex organic transistor circuits for detection in tumor cell cultures. We finally show the versatility of organic electronic materials and devices by demonstrating other sensing strategies such as nucleic acid detection using a simple biofunctionalization approach. Although the focus is on in vitro metabolite monitoring, the findings generated throughout this work can be extended to a variety of other sensing strategies as well as to applications including on body (wearable) or even in vivo sensing.

<p>During the last 30 years a new research and technology field of organic electronic materials has grown thanks to a groundbreaking discovery made during the late 70’s. This new field is today a worldwide research effort focusing on exploring this new class of materials that also enable many new areas of electronics applications. In the organic electronics research field conducting organic molecules and polymers are synthesized and used in devices. The reason behind the success of conducting polymers is the flexibility to develop materials with new functionalities via clever chemical design and the possibility to use low-cost production techniques to manufacture devices.</p><p>This thesis reviews and describes different aspects of the organic electronics, here focusing on electrochromic displays; device improvements, the study of degradation and also patterning technology for rational manufacturing processing. The color contrast in electrochromic displays based on conjugated polymers was increased with approximately a factor of two by adding an extra electrochromic polymer. It was found that electrochemical over-oxidation (ECO) limits the flexibility in choosing desired electrochromic materials. ECO is one of the main degradation mechanisms in electrochromic displays. ECO is an efficient and fast process to permanently reduce the electronic conductivity in polythiophenes. From this, a novel patterning process was developed, in which the films of polythiophenes can be patterned through local and controlled deactivation of the conductivity. The ECO has been combined with different patterning tools to enable the use of existing printing tools for manufacturing. In combination with screen-printing, low-cost and high volume roll-to-roll patterning was demonstrated, while together with photolithography, patterning down to 2 µm can be achieved. Systematic studies have shown that conductivity contrasts beyond 107 can be achieved, which is enough for various simple electronic systems. To generate better understanding of the ECO phenomena the effect of pH on the over-oxidation characteristics was studied. The results suggest that a part of the mechanism for over-oxidation depends on the OH– concentration of the electrolyte used.</p>

<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>

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.

Silicon is the most important semiconducting material for optoelectronics owing to its suitable and tunable physical properties. Even though there are several alternatives, silicon based solar cells are still the most widely produced and commercially feasible system. Extensive efforts have been spent in order to increase the efficiency and decrease the cost of these systems. The studies that do not focus on replacement of the semiconducting material, mostly concentrate on the developments that could be brought by nanotechnological approaches. In this aspect, utilization of silicon nanowires has been predicted to improve the efficiency of the silicon based solar cell technology. Moreover, besides solar cells, silicon nanowires have been investigated for many other electronic systems such as thermoelectrics, light emitting diodes, biological/chemical sensors, photodetectors and lithium ion v batteries. Therefore, production of silicon nanowires through a cost-effective and well controlled method could make important contributions to many fields. In this thesis, electroless etching method, which is a novel and solution based method enabling vertically aligned silicon nanowire array fabrication over large areas, is investigated. A detailed parametric study resulting in a full control over the resultant nanowire morphology is provided. The parameters affecting the structure have been determined as etching time, solution temperature, solution concentration, pressure and starting wafer characteristics. The results show that electroless etching method could replace the conventional silicon nanowire fabrication methods. It was shown that specific nanowire lengths for any application, can be obtained simply by adjusting the parameters of electroless etching system. One of the most crucial features of vertically aligned silicon nanowire arrays is their remarkable antireflective properties. The optical reflectivity measurements showed that 42% reflectivity of pristine polished silicon wafer decreases down to 1% following fabrication of silicon nanowire arrays on their surface. This unique characteristic reveals that these nanowires could be used as antireflective surfaces in solar cells. Moreover, it was determined that p-n heterojunctions that are formed by silicon nanowires, namely radial heterojunctions, would yield higher efficiencies compared to planar heterojunctions because of the dramatic increase in the charge carrier collection efficiency and orthogonal photon absorption. On this subject, n-type silicon nanowire arrays were fabricated by electroless etching followed by drop casting Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT:PSS) organic layer on these nanowires as the complementary layer, forming the radial heterojunction. The energy conversion efficiency of silicon nanowire / PEDOT: PSS device was found as 5.30%, while planar silicon / PEDOT: PSS control device displayed only 0.62% efficiency. Developments and optimizations in both the electroless etching method and solar cell models could lead to important developments in photovoltaic industry.

No description available.

The development of a complete thermoelectric generator and its application on a display polarizer film was successfully accomplished in this thesis. A systematic study of the prospective thermoelectric materials, PEDOT:PSS-based and ${ZnON}$, used for the present application is presented. To the best of our knowledge, this is the first exploration of the thermoelectric parameters of ${ZnON}$ reported here. Thin-film deposition of these materials was performed via both solution- and vacuum-based techniques. In addition, certain doping mechanisms were tested in an attempt to further understand the correlation between electrical conductivity and Seebeck coefficient. A maximum power factor of $42{\mu}Wm^{-1}K^{-2}$ was achieved for the PEDOT:PSS-based thin film at room temperature. It was initially doped via 5vol% of DMSO and sequentially treated with ethylene glycol. Specifically, its electrical conductivity displayed a 2-fold increase after EG treatment, reaching a value of about 1632 Scm$^{-1}$. Systematic studies performed on the association between thin-film thickness and its Seebeck coefficient shows a decrease in the latter as the number of multilayers printed increases. Among the different $O_{2}/N_{2}$ ratios that were tested for ${ZnON}$ thin films, a maximum power factor value of 163${\mu}Wm^{-1}K{-2}$ was achieved with the lowest $O_{2}$ flow rate configuration. In contrast to PEDOT:PSS-based thin films, the ${ZnON}$ displayed the opposite effect on the relation of the Seebeck coefficient with respect to thin-film thickness. Furthermore, a heterostructure was also developed by implementing ${ZnO}$ nanowires into the ${ZnON}$ thin film. ${ZnO}$ nanowires have been fabricated through the hydrothermal method on inkjet-printed patterns of zinc acetate dihydrate. It has been demonstrated that with the right inkjet-printing parameters and substrate temperature, ${ZnO}$ nanowires can be effortlessly fabricated in accordance with the desired pattern variations under low temperature and mild conditions. Finally, a complete device of the thermoelectric generator was fabricated using the above materials and a special set-up developed in order to test the device on the polarizer. The power output achieved from a 1-thermoelectric couple under normal backlight illumination and ambient conditions was 23pW. Overall, it is thought that the particular design and proof of concept presented here can be the basis of a prospective energy harvesting scheme via thermoelectrics in future display-based handheld devices.

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No. of bitstreams: 1 klem_ms_me_bauru.pdf: 4012228 bytes, checksum: f1af56b8b0b9f5e19934e197b4755874 (MD5) Previous issue date: 2017-09-27 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Realizou-se primeiramente neste trabalho o estudo de um supercapacitor padrão utilizando coletores de aço inox e eletrodos de grafite Aquadag®. Este dispositivo apresentou uma capacitância máxima de 22 F/g, e seu espectro de impedância foi modelado por um circuito do tipo R(C(RW))(RC)(RC). Com este dispositivo foi possível testar os métodos de produção dos supercapacitores, e identificar as características desejáveis no supercapacitor impresso. Foram testadas duas técnicas de impressão distintas visando o preparo de eletrodos e coletores de corrente impressos em papel para aplicação em supercapacitores. O material ativo utilizado nos eletrodos foi basicamente o PEDOT:PSS, com a adição de óxido de grafeno, grafite aquadag® e nanotubos de carbono de paredes múltiplas (MWNT) para a formação compósitos condutores. Foram realizadas caracterizações morfológicas e elétricas nas superfícies dos eletrodos impressos em papel filtro, vegetal e sulfite. Os eletrodos produzidos por serigrafia utilizando o compósito de PEDOT:PSS com MWNT impressos em papel filtro apresentaram os menores resultados de resistência de folha (17 Ω/sqr), sendo assim utilizados na produção dos supercapacitores. O supercapacitor impresso em papel apresentou um bom comportamento capacitivo através de medidas de espectroscopia de impedância e voltametria cíclica. A curva de impedância foi modelada através de um circuito do tipo R(RC)(C(RQ))(RC), evidenciando uma alta capacitância de dupla camada. Foi encontrada uma capacitância específica máxima de 20,3 F/g.para uma corrente de carga/descarga de 1 mA, e uma resistência equivalente em série de 60 Ω. Estes valores levaram a densidades de energia e potência de 3,1 Wh/kg e 420 W/kg, respectivamente. Realizaram-se também simulações e ajustes a partir das análises em corrente contínua, usando um circuito equivalente RC paralelo com uma resistência em série. Através destes ajustes foi possível extrair parâmetros de grande importância na utilização prática dos supercapacitores. / In this study, we first produced a standard supercapacitor using stainless steel collectors and Aquadag® graphite electrodes. The device exhibited a maximum capacitance of 22 F/g, and an R(C(RW))(RC)(RC) circuit modeled its impedance spectrum. With this device was possible to test the production methods of supercapacitors, and identify its desirable characteristics. Two different printing techniques were tested to produce electrodes/current collectors. The active material used in the electrodes was PEDOT: PSS, with addition of graphene oxide, Aquadag® graphite and multi-walled carbon nanotubes (MWNT), in order to obtain conductive composites. Morphological and electrical characterizations were performed over the surfaces of printed electrodes onto filter, vegetable and bond paper. The electrode produced by screen-printing using the PEDOT: PSS/MWNT composite printed onto filter paper exhibited low sheet resistance (17 Ω /sqr), being used in the production of supercapacitors. Printed supercapacitor showed good capacitive behavior through impedance spectroscopy and cyclic voltammetry measurements. An R(RC)(C(RQ)(RC) circuit modeled the impedance spectrum, evidencing a high double layer capacitance. A maximum specific capacitance of 20.3 F / g was found for a charge/discharge current of 1 mA, and an equivalent series resistance of 60 Ω. These values led to energy and power densities of 3.1 Wh / kg and 420 W / kg, respectively. Simulations and curve fitting were also performed from DC analyzes, using a parallel RC circuit coupled with a series resistance, obtaining important parameters for the practical use of supercapacitors. / FAPESP: 2015/18091-8

De nos jours, le domaine biomédical est en pleine croissance avec le développement de dispositifs thérapeutiques innovants, bas coût, pour le diagnostic, le traitement ou la prévention de maladies chroniques ou cardiovasculaires. Ces dernières années ont connu l’émergence des polymères semi-conducteurs, alternative intéressante aux matériaux inorganiques, présentant des propriétés uniques de conduction ionique et électronique. Tout d’abord, j’ai axé mes travaux de recherche sur le développement et l’optimisation d’une encre conductrice à base de PEDOT:PSS, parfait candidat comme matériau, pour la transduction des signaux biologiques en signaux électriques, compatible avec le process jet d’encre, pour la réalisation de dispositifs imprimés. Puis mes travaux se sont orientés vers la conception et l’étude d’électrodes imprimées sur supports papiers, tatous et textiles permettant des enregistrements long termes d’électrocardiogrammes (ECG) ou électromyogrammes (EMG), présentant des performances similaires aux électrodes commerciales, utilisant un système d’acquisition spécifique pour la mesure d’activités électriques de tissus musculaires. Puis dans un second temps, je me suis penchée sur l’impression sur support papier, de transistors organiques électrochimiques (OECTs) fonctionnalisés, afin de permettre la détection d’éléments biologiques ou chimiques comme l’alcool. Ces travaux proposent une nouvelle voie pour la conception de dispositifs innovants biomédicaux à bas couts, imprimés, permettant la personnalisation des produits pouvant être intégrés dans des dispositifs biomédicaux portables ou dans des vêtements « intelligents ». / With the evolution of microelectronics industry and their direct implementation in the biomedical arena, innovative tools and technologies have come to the fore enabling more reliable and cost-effective treatment. In this thesis I focus on the integration of the conducting polymer PEDOT:PSS with printing technologies toward the realization of performant biomedical devices. In the first part, I focus on the optimization of the conducting ink formulation. Following, I emphasize on the fabrication of inkjet printed PEDOT:PSS based biopotential electrodes on a wide variety of substrates (i.e., paper, textiles, tattoo paper) for use in electrophysiological applications such as electrocardiography (ECG) and electromyography (EMG). Printed electrodes on paper and printed wearable electrodes were fabricated and investigated for long-term ECG recordings. Then, conformable printed tattoo electrodes were fabricated to detect the biceps activity during muscle contraction and the conventional wiring was replaced by a simple contact between the tattoo and a similarly ink-jet printed textile electrode.In the last part, I present the potentiality of inkjet printing method for the realization of organic electrochemical transistor (OECTs) as high performing biomedical devices. A disposable breathalyzer comprised of a printed OECT and modified with alcohol dehydrogenase was used for the direct alcohol detection in breath, enabling future integration with wearable devices for real-time health monitoring. Their compatibility with printing technologies allows the realization of low-cost and large area electronic devices, toward next-generation fully integrated smart biomedical devices.