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Solution-processed organic field effect transistors (OFETs) have emerged in recent years as promising contenders to be part of electronic and optoelectronic circuits owing to their compatibility with low-cost high throughput roll-to-roll manufacturing technology. The stringent performance requirements for OFETs in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require the performance of single crystal-based OFETs, but these suffer from major scale-up challenges. To achieve device performance approaching that of single crystals with scalable, high throughput and industry-compatible solution coating of OFETs requires understanding and ultimately controlling the crystallization of organic semiconductors (OSCs), and producing very low defect-density thin films. In this thesis, we develop an understanding of the process-structure-property-performance relationship in OSCs that bring fresh insights into the nature of solution crystallization and lead to novel ways to control OSC crystallization, and finally help achieve fabrication of high-performance OFETs by scalable, high throughput and industry-compatible blade coating method. We probe the solution crystallization of OSCs by employing a suite of ex & in situ characterization techniques. This leads us to an important finding that OSC molecules aggregate to form a dense amorphous intermediate state and nucleation happens from this intermediate state during blade coating under a wide window of coating conditions. This phenomenon resembles the so-called two-step nucleation model. Two-step nucleation mediates the crystallization of a wide range of natural and synthetic products ranging from soft materials, such as proteins, biominerals, colloids and pharmaceutical molecules, to inorganic compounds. We go on to show that this nucleation mechanism is generally applicable to achieve formation of high-quality polycrystalline films in a variety of small molecule OSCs and their polymer blends. This phenomenon results in highly textured and well-connected domains, which exhibit reduced interfacial and bulk trap-state densities, helping raise the carrier mobility by one to two orders of magnitude in OFETs in comparison to direct nucleation. We extend the understanding developed for solution crystallization of various acenes and thiophene-based small molecule OSCs to the high-performance benzothieno-benzothiophene (BTBT) based small molecule OSCs. On this end, we develop protocols to fabricate high-quality thin films of BTBT based OSCs by blade coating at industrially compatible coating speeds (>100 mms-1). These films show massive single-domains with very few apparent defects when crystallized via multiple liquid-crystalline phases in two-step nucleation conditions, resulting in an average carrier mobility of ~10 cm2V-1s-1. To sum up, this thesis develops an understanding of OSC solution crystallization and efficient protocols to control polycrystalline thin film quality for high-performance OFETs. These protocols involve a combination of two-step nucleation pathway, solvent mixtures, polymer blends and device-manufacturing conditions. Our efforts enable to realize high-performance OFETs based on high-quality polycrystalline OSC thin films at industry-compatible conditions.

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

abstract: Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are a lot more flexible in comparison. In this work, it was observed that not any α-alumina could be used by the blade coating process to get a good quality separator on Li4Ti5O12 (LTO) electrode. In this work specifically, the effect of particle size of α-alumina, on processability of slurry was investigated. The effect of the particle size variations on quality of separator formation was also studied. Most importantly, the effect of alumina particle size and its distribution on the performance of LTO/Li half cells is examined in detail. Large-sized particles were found to severely limit the ability to fabricate such separators. The α-alumina slurry was coated onto electrode substrate, leading to possible interaction between α-alumina and LTO substrate. The interaction between submicron sized particles of α-alumina with the substrate electrode pores, was found to affect the performance and the stability of the separator. Utilizing a bimodal distribution of submicron sized particles with micron sized particles of α-alumina to prepare the separator, improved cell performance was observed. Yet only a specific ratio of bimodal distribution achieved good results both in terms of separator formation and resulting cell performance. The interaction of α-alumina and binder in the separator, and its effect on the performance of substrate electrode was investigated, to understand the need for bimodal distribution of powder forming the separator. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

Les fluides à seuil sont des matériaux utilisés dans de nombreux procédés industriels au cours desquels ils sont mis en écoulement via leur interaction avec des outils solides. Afin de mieux comprendre comment ils s'étalent sur des surfaces, nous avons étudié d'une part leur enduction verticale sur une plaque mince et d'autre part leur étalement horizontal à l'aide d'une lame. Ces deux études se sont appuyées sur des mesures macroscopiques permettant de suivre la force appliquée à l'outil et des mesures microscopiques de PIV pour déterminer les champs de vitesse dans le matériau. Après confirmation de leur validité par comparaison avec nos résultats expérimentaux, des simulations numériques basées sur la programmation conique ont permis de préciser les écoulements en jeu. Pour l'enduction par trempage, nous observons que dans notre gamme d'étude, le dépôt de fluide à seuil sur la plaque est millimétrique et d'épaisseur constante, sauf aux extrémités. Selon le rapport des forces visqueuses et plastiques, l'enduction est régie par un équilibre "seuillo-gravitaire" ou "visco-gravitaire". Nous avons ensuite caractérisé l'écoulement généré dans le bain par le déplacement de la plaque afin d'expliciter l'origine du phénomène d'enduction. Les simulations numériques précisent la forme de cet écoulement. L'étalement horizontal dans un canal à l'aide d'une lame mince conduit au déplacement d'un amas de fluide faiblement cisaillé par rapport à une région de fluide au repos, par l'intermédiaire d'une couche cisaillée. Nous montrons qu'un modèle simple permet de prédire la dynamique de croissance de l'amas et la relie à la force normale à la lame / Yield stress fluids are used in various industrial processes in which solid tools make them flow. To have a better understanding on how they spread on surfaces, we first studied the vertical coating on a thin plate and then the horizontal blade-coating. Both studies are based on macroscopic measures recording the force applied on the plate and on the microscopic determination on the velocity fields in the fluid by PIV. Numerical simulations based on cone programming, which validity had been confirmed in comparison to our experimental results, specified the flows at stake. In dip-coating, we observed than within our framework, the yield stress fluid deposit on the plate is millimetric and of constant thickness, except on the tips. According to the value of the viscous over plastic forces ratio, the coating is led by a "yield-gravity" or a "visco-gravity" balance. Then, we characterized the flow generated in the bath by the plate displacement in order to clarify the origin of the coating phenomenon. The numerical simulations specified the flow characteristics. The horizontal blade-coating in a channel involves the displacement of a weakly sheared cluster of fluid in relation to a part of fluid at rest, through a sheared layer. We showed that the growing dynamic of the cluster is described with a simple model which links it to the normal force to the plate

This thesis investigates novel hole extraction interfaces and series interconnects for applications in organic photovoltaics, specifically in single junction solid-state dye-sensitized solar cells (DSSCs) and tandem DSSC/polymer bulk heterojunction solar cells. Improvements in hole extraction and device performance by using materials compatible with scalable deposition methods are presented, including tungsten- and molybdenum-disulphide (WS₂ and MoS₂), and p-type doped spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) nanoparticle dispersions. WS₂ and MoS₂ hole extraction layers increase averaged short circuit currents by 20% and 16% respectively, and power conversion efficiencies by 19% and 14% respectively when compared with control devices. Similarly, doped spiro-OMeTAD nano-particle layers improved short circuit current densities by 32% and efficiencies by 9%. Tandem device interconnects using these novel hole extraction formats have been fabricated, but although devices did exhibit rectification, overall performance was poor. Possible reasons for their limited success have been analysed. Dye-sensitized solar mini-modules are also reported. In order to assure the scalability of DSSC technology, these larger area devices were constructed using doctor blade coating to deposit the hole transporter material. As well as achieving a respectable maximum power conversion efficiency of 2.6%, it has also been shown that the extent to which hole transporter infiltrates the mesoporous photoanode of these devices may be tuned by altering substrate temperature during deposition. It was found that an optimal coating temperature of 70 degrees C produced the best efficiency, with a corresponding pore-filling fraction of 41%.

Considerable attention has been focused on nanomaterials and their extensive applications. Metallic nanoparticles, especially gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs), due to their superior physical, chemical, and optical properties, are vastly developed for numerous biomedical applications such as drug and gene delivery systems, diagnostic biosensors, imaging, and therapeutics. This study presents a low-cost method for the fabrication of self-assembled metallic nanoparticles, including gold and silver, via a reactive blade coating process, which is carried out based on in situ reduction of the metal precursors. This technique is a roll-to-roll compatible technique suitable for scalable nanomanufacturing. Oleylamine was used as a reducer agent, and gold (III) chloride hydrate and silver salts, including silver nitrate and silver perchlorate hydrate, were used as the metal precursors. Fabrication was carried out by first blade coating the reducer ink and subsequently coating the precursor ink followed by 3 hours of heat treatment. Various solvent systems were used to examine the effect of different solvents on the fabrication process. Surface morphology, crystalline phase composition, and plasmon resonance of the coated samples were characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), and UV-Vis spectroscopy, respectively. Results demonstrated the synthesis of spherical self-assembled AuNPs using toluene (TOL) and isopropyl alcohol (IPA) for reducing and precursor solvents, respectively. Changing the concentration of reactants or increasing the coating layers exhibited a change in the average size of AuNPs. Self-assembled AuNPs thin films were also demonstrated to have the potential to be used as a biosensing platform based on localized surface plasmon resonance (LSPR) effect to detect the elevated levels of glucose in an aqueous solution. Recently, the world has faced a pandemic of Covid-19 caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which has threatened human health and has brought a worldwide devastating economic and social crisis. Hence, finding a solution to mitigate the current breakout of Covid-19 is vital to protect the international community from its causing harm. AgNPs as an antimicrobial agent, which has exhibited promising antiviral activity against several viruses, can offer a resolution to combat the spread of Covid-19. In this regard, AgNPs thin films were fabricated analogously via blade coating using various reducer and silver salt inks made of different solvent systems. Virucidal efficacy of reactive blade coated AgNPs on glass substrates was analyzed against human coronavirus 229E, a virus from the Coronavirus family, as a surrogate SARS-CoV-2 (according to the Level 2 Biosafety facility at uOttawa). Plaque forming assay indicated more than 99.99% reduction in infectivity of the virus when it contacts the AgNPs coated glass for 30 min before infecting cells. These results suggest the excellent potential for reactive blade coated AgNPs as an antiviral agent against coronavirus to avoid the spread of the virus.

Ce travail de thèse porte sur l'étalement de fluides complexes. Il met en évidence la riche phénoménologie d'un acte simple : celui d'étaler avec un racloir (rigide ou souple) une émulsion ou une solution de polymères sur un substrat. Pour chacun des fluides modèles étudiés, nous nous sommes focalisés expérimentalement sur l'observation de l'écoulement au cours de l'entraînement de la solution. Dans des conditions données d'étalement, il apparaît qu'une émulsion o/w peut s'inverser via plusieurs mécanismes de déstabilisation, ou encore, dans le cas d'une solution de polymères, exhiber une instabilité de sa ligne de contact, donnant naissance à des filaments de tailles et de longueurs d'ondes spécifiques. Nous montrons que les différents paramètres d'étalement, comme par exemple la hauteur du racloir, la vitesse d'étalement, les propriétés du substrat ou encore la rhéologie des solutions, doivent être pris en compte pour construire des diagrammes de phase d'étalement séparant les domaines d'existence des instabilités observées (régime de recouvrement partiel), des domaines où la solution transite vers le recouvrement total du substrat. D'autre part, nous tirons l'avantage de ces instabilités pour nous permettre de déposer de façon contrôlée des structures variées, offrant d'intéressantes perspectives en termes d'applications. / This study shows the rich phenomenology of a simple act : spreading complex solutions such as emulsion and polymer solution on a plate, by using a rigid and flexible blade respectively. Here, we experimentally study the flow of the solution over the course of its spreading. During the spreading and in certain conditions, different phenomena occur, namely, emulsion inversion in the case of o/w emulsion or a contact line instability in the case of the polymer solution, which gives rise to the formation of polymer filaments with a well-defined wavelength and characteristic sizes. We showed, thanks to spreading phase diagrams, that the the existence of the instability (partial wetting regime) is separated to a domain where the solution cover the substrate. Spreading parameters such as the height of the scraper, spreading velocity or properties of the fluids turns out to be crucial. Finally, we take advantage of the instabilities to print a variety of interesting patterns for further applications.

No description available.