Today’s state of the art additive manufacturing (AM) systems have the ability to fabricate multi-material devices with novel capabilities that were previously constrained by traditional manufacturing. AM machines fuse or deposit material in an additive fashion only where necessary, thus unlocking advantages of mass customization, no part-specific tooling, near arbitrary geometric complexity, and reduced lead times and cost. The combination of conductive ink micro-dispensing AM process with hybrid manufacturing processes including: laser machining, CNC machining, and pick & place enables the fabrication of printed electronics. Printed electronics exploit the integration of AM with hybrid processes and allow embedded and/or conformal electronics systems to be fabricated, which overcomes previously limited multi-functionality, decreases the form factor, and enhances performance. However, AM processes are still emerging technologies and lack qualification and standardization, which limits widespread application, especially in harsh environments (i.e. defense and industrial sectors). This dissertation explores three topics of electronics integration into AM that address the path toward qualification and standardization to evaluate the performance and repeatable fabrication of printed electronics for resilience when subjected to harsh environments. These topics include: (1) the effect of smoothing processes to improve the as-printed surface finish of AM components with mechanical and electrical characterization—which highlights the lack of qualification and standardization within AM printed electronics and paves the way for the remaining topics of the dissertation, (2) harsh environmental testing (i.e. mechanical shock, thermal cycling, die shear strength) and initiation of a foundation for qualification of printed electronic components to demonstrate survivability in harsh environments, and (3) the development of standardized methods to evaluate the adhesion of conductive inks while also analyzing the effect of surface treatments on the adhesive failure mode of conductive inks. The first topic of this dissertation addresses the as-printed surface roughness from individually fusing lines in AM extrusion processes that create semi-continuous components. In this work, the impact of surface smoothing on mechanical properties and electrical performance was measured. For the mechanical study, surface roughness was decreased with vapor smoothing by 70% while maintaining dimensional accuracy and increasing the hermetic seal to overcome the inherent porosity. However, there was little impact on the mechanical properties. For the electrical study, a vapor smoothing and a thermal smoothing process reduced the surface roughness of the surfaces of extruded substrates by 90% and 80% while also reducing measured dissipative losses up to 24% and 40% at 7 GHz, respectively. The second topic of this dissertation addresses the survivability of printed electronic components under harsh environmental conditions by adapting test methods and conducting preliminary evaluation of multi-material AM components for initializing qualification procedures. A few of the material sets show resilience to high G impacts up to 20,000 G’s and thermal cycling in extreme temperatures (-55 to 125ºC). It was also found that coefficient of thermal expansion matching is an important consideration for multi-material printed electronics and adhesion of the conductive ink is a prerequisite for antenna survivability in harsh environments. The final topic of this dissertation addresses the development of semi-quantitative and quantitative measurements for standardizing adhesion testing of conductive inks while also evaluating the effect of surface treatments. Without standard adhesion measurements of conductive inks, comparisons between materials or references to application requirements cannot be determined and limit the adoption of printed electronics. The semi-quantitative method evolved from manual cross-hatch scratch testing by designing, printing, and testing a semi-automated tool, which was coined scratch adhesion tester (SAT). By cross-hatch scratch testing with a semi-automated device, the SAT bypasses the operator-to-operator variance and allows more repeatable and finer analysis/comparison across labs. Alternatively, single lap shear testing permits quantitative adhesion measurements by providing a numerical value of the nominal interfacial shear strength of a coating upon testing while also showing surface treatments can improve adhesion and alter the adhesive (i.e. the delamination) failure mode of conductive inks.

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>

Several challenges are still holding back the technological transfer of printed electronics to industry in spite of recent progresses. In this thesis work, the printing method of inks based on silver nanoparticles (<Ø>=25 nm) was optimized according to its rheology and to the fluid/substrate interactions for the fabrication of electrical interconnections with a thickness of 500 nm. These lines were printed on silicon or flexible substrates and annealed either by conventional (oven or infrared) or selective methods (microwave) at temperatures comprised between 100 and 300 °C.A better understanding of the relationship between process and microstructure of these printed thin films, based on several crystallographic equipments (XRD, EBSD and EDX), led to the optimization of nanocrystallites growth with an activation energy of about 3 to 5 kJ*mol-1. In addition to the low residual stress (70 MPa), this optimization is used to achieve low electrical resistivity (3.4 μOhm*cm) associated with a greater coherence of the crystal lattices at grain boundaries. The probability of electron scattering at such interfaces can be further reduced using an innovative approach of oriented crystallite growth by atomic interdiffusion from the substrate.The low mechanical stiffness (E<50 GPa) of these porous lines requires a reinforcement step either by crystalline texturation or by electroless growth to withstand the assembly and wire-bonding steps. The fabrication of a functional demonstrator thus validated the printing technology for the manufacture of electronic components.

Thin film copper indium gallium selenide (CIGS) solar cells have exhibited single junction power conversion efficiencies above 20% and have been commercialized. The large scale production of CIGS solar cells, however, is hampered by the relatively high cost and poor stoichiometric control of coevaporating tertiary and quaternary semiconductors in high vacuum. To reduce the overall cost of production, CIGS nanocrystals with predetermined stoichiometry and crystal phase were synthesized in solution. Colloidal nanocrystals of CIGS provide a novel route for production of electronic devices. Colloidal nanocrystals combine the well understood device physics of inorganic crystalline semiconductors with the solution processability of amorphous organic semiconductors. This approach reduces the overall cost of CIGS manufacturing and can be used to fabricate solar cells on flexible and light-weight plastic substrates. As deposited CIGS nanocrystal solar cells were fabricated by ambient spray-deposition. Devices with efficiencies of 3.1% under AM1.5 illumination were fabricated. Examining the external and internal quantum efficiency spectrums of the devices reveal that in nanocrystal devices only the space charge region is actively contributing to the extracted photocurrent. The device efficiency of the as-deposited nanocrystal films is presently limited by the small crystalline grains (≈ 15 nm) in the absorber layer and the relatively large interparticle spacing due to the organic capping ligands on the nanocrystal surfaces. Small grains and large interparticle spacing limits high density extraction of electrons and holes from the nanocrystal film. A Mott-Schottky estimation of the space charge region reveals that only 50 nm depth of the nanocrystalline absorber is effectively contributing to the photogenerated current. One strategy to improve charge collection involves increased space charge region for extraction by vertical stacking of diodes. A much longer absorption path for the photons exists in the space charge region with the stacked devices, increasing the probability that the incident radiation is absorbed and then extracted. This method enables an increase in the collected short circuit current. The overall device efficiency, however, suffers with the increased series resistance and shunt conductance of the device. Growth of nanocrystal grains was deemed necessary to achieve power conversion efficiencies comparable to vapor deposited CIGS films. Simple thermal treatment of the nanocrystal layers did not contribute to the growth of the crystalline grain size. At the same time, because of the loss of selenium and increased trap density in the absorber layer, there was a measurable decrease in device efficiency with thermal processing. For increased grain size, the thermal treatment of the absorber layer took place in presence of compensating amounts of selenium vapor. The process of selenization, as it is called, took place at 500°C in a graphite box and led to an increase of the grain size from 15 nm to several microns in diameter. Devices with the increased grain size yielded efficiencies up to 5.1% under AM1.5 radiation. Mott-Schottky analysis of the selenized films revealed a reduction in doping density and a comparable increase in the space-charge region depth with the increased grain size. The increased collection combined with the much higher carrier mobility in the larger grains led to achieved Jsc values greater than 20 mA/cm2. Light beam induced current microscopy (LBIC) maps of the devices with selenized absorber layers revealed significant heterogeneity in photogenerated current. Distribution of current hotspots in the film corresponded with highly selenized regions of the absorber films. In an effort to improve the overall device efficiency, improvements in the selenization process are necessary. It was determined that the selenization procedure is dependent on the selenization temperature and processing environment. Meanwhile, the reactor geometry and nanocrystal inks composition played important roles in determining selenized film morphology and the resulting device efficiency. Further work is necessary to optimize all the parameters to improve device efficiency even further. / text

The aim of this master thesis was to develop a process for fabricating Schottky diodes, using techniques that are suitable for cheap large volume mass production e.g. printing, with tetrapod structured ZnO as the semiconductor. Part of the work involved selecting suitable metals for ohmic and Schottky contact and identification of a binder that can be used for dispersion of the Zinc Oxide (ZnO). ZnO is a II-VI compound semiconductor with a wide band gap (3,4 eV). The Schottky diode is used as a rectifier. A rectifier serves the purpose to turn Alternating Current (AC) to Direct Current (DC). The Schottky diode should only conduct current in the forward direction, in the reverse direction the current should be blocked. In this thesis printed diodes were used to construct different types of rectifiers for example half wave rectifiers and full wave rectifiers. Aside from electrical properties, adhesion properties have also been investigated. Adhesion was showed to depend on not only the choice of binder, but also UV-dose and annealing temperature. Aluminum and silver together with ZnO proved to be the best materials combination with a rectification ratio up to 105−106. Different sizes of Schottky diodes were printed and the smaller diodes with an area of 0,5x0,5mm^2 performed best as a half wave rectifiers while the larger size,1x1mm^2, performed best as a full wave rectifier.

Gravure printing is a conventional printing process used for printing graphics on products ranging from magazines and packaging to wallpaper and floor coverings. It is a versatile process that can be used to deposit a variety of fluid materials onto many different surfaces. It is also capable of very high speed deposition, with speeds up to 60 m/min being reported. Because of its versatility and high throughput capability, gravure is an attractive platform for the manufacture of devices composed of relatively thin layers of functional, electronic materials deposited onto flexible substrates. In many cases, these materials can be deposited in liquid form, in which case gravure printing can potentially be used. One such material that is commonly used is Indium Tin Oxide (ITO), a transparent, conducting ceramic material. It is commonly deposited onto flexible, transparent polyethylene terapthalate (PET) films that can be used in flexible displays, solar cells, and other devices requiring a transparent, conducting layer. This thesis examines the effect of key process parameters on the physical and functional characteristics of a printed ITO nanoparticle layer. ITO layers were successfully printed that were between 300 and 1300 nm thick, with roughness Ra generally less than a few hundred nm. The sheet resistance values were relatively high, in the hundreds of kohms/square. The transparency was relatively low, although the films were generally transparent. Several parameters were found to be significant in affecting the several different physical and performance measures, specifically solvent and ITO content, as well as cell geometry.

There is a great demand for low-cost disposable sensors in a variety of markets, such as the food chainand health care. No assay is performed more than that of glucose and approximately 85 % of the entirebiosensor market accounts for glucose biosensors. Each year, 6 billion glucose assays are performed andthe majority of them are based on electrochemical detection. Organic electrochemical transistors(OECTs) have favorable properties in terms of low operating voltages and have previously been used asbase for electrochemical detection of glucose. A low-cost disposable biosensor can be achieved by theuse of high throughput printing techniques. Up until now, no printable biosensors based on organic electrochemicaltransistors have been developed. In this thesis a printable miniaturized prototype for a glucose biosensor based on an OECT with a platinizedgate electrode has been designed, developed and evaluated. The biosensor has been functionalizedwith the enzyme glucose oxidase. Different platinum deposition techniques have been used to depositplatinum onto the printed carbon gate electrode: electrodeposition, platinum nanoparticle solutiondeposited either by inkjet printing or pipetting and thermal evaporation. The gate electrodes were characterized with cyclic voltammetry in hydrogen peroxide, ferricyanide andglucose. The characterizations revealed no significant differences between the different deposition techniques.However, with gate electrodes produced by printed carbon followed by electrodeposition ofplatinum it was possible to sense glucose in a concentration in the range of the values for diabetic persons.Thus, the electrodes are a promising option as gate electrodes in a glucose biosensor based on anOECT. The characteristics of the OECT revealed that the responses resembled a transistor.

Ce projet vise à développer de nouvelles encres à base de nanofils d’argent et de nanocellulose pour des applications conductrices et transparentes. Les nanocelluloses, nanoparticules issues de la cellulose, sont de deux types : les nanocristaux de cellulose (NCC) et les nanofibrilles de cellulose (NFC) et possèdent des propriétés bien spécifiques. Ce travail a consisté d’une part (i) à utiliser la forme tubulaire et rigide des NCC pour produire des nanotubes d’argents par synthèse chimique, avant leur formulation en encre et d’autre part (ii) à utiliser les propriétés d’enchevêtrement des NFC flexibles pour stabiliser des nanofils d’argent commerciaux, habituellement instables en suspension. Les divers résultats de ce projet ont permis d’aboutir à la formulation brevetée et à la commercialisation d’une encre conductrice à base d’une faible quantité d’argent et de NCC et de deux encres conductrices et transparentes à base de NFC et de nanofils d’argent. Les interactions physico-chimiques et la stabilité colloïdale de ces suspensions hybrides ont été étudiée de manière fondamentale, tout en développant des formulations adaptées à divers procédés d’impression, que ce soit à échelle laboratoire mais aussi industrielle. / This project aims at developing new conductive inks based on nanocellulose and silver nanowires for transparent and conductive applications. Nanocellulose are nanoparticles extracted from the cellulose and two kinds currently exist: the cellulose nanocrystals (CNC) and the cellulose nanofibrils (CNF). This project have evaluated on one hand the ability of using tubular rigid CNC as template for producing silver nanorods, prior their formulation into conductive inks. On the other hand, the ability of using flexible and entangled CNF to stabilize commercial silver nanowires, usually unstable in suspension, was investigated. The results of this project lead to the patented formulation and commercialization of one low silver content conductive ink based on silver and CNC and two conductive transparent ink based on CNF and silver nanowires. Physico-chemical interactions and colloidal stability of such hybrid suspension have been scientifically studied meanwhile printing process adapted formulation have been successfully designed and tested at laboratory scale but also industrial scale.

This thesis was conducted to provide an automated method for characterization of printed electronics. The work was built on a multi-axis milling machine. Further, the machine was modified by replacing the milling-tool with an installment utilizing electrical probing. Different measurement techniques, machine vision applications, and software solutions were evaluated and utilized. All the revolving functionalities of this project was then merged into a complete system, controlled by a graphical user interface. The resulting system was capable of autonomously characterize a given number of components on a printed sheet. The final version of the system is capable of finding the origin of the sheet by using machine vision and fiducial markers.

Abstract This thesis investigates the reliability of printed conductors on flexible substrates under cyclic bending. The topic is approached by studying the effects of several key design parameters on the bending lifetime of printed conductors under dynamic loading. In this thesis, the test specimens with various cross-sectional geometries were printed on different plastic and paper substrates. The test samples were fabricated with two printing methods, silk screen and roll-to-roll printing, by utilizing three different silver pastes as the conductive material. To evaluate the long-term performance of the printed traces, the test specimens were exposed to cyclic bending and their electrical behaviour during the test was monitored with resistance measurements. The bending test results were analysed by utilizing the Weibull analysis, with a 20% increase in resistance as the failure criterion. This method yielded a characteristic lifetime for a test population, including 10 individual test specimens. When comparing the characteristic lifetimes of all of the fabricated test populations, it was observed that all of the varied design parameters had an effect on the bending reliability of the printed traces. However, within the studied geometries and materials, the substrate was found to have the highest impact on the long-term electrical performance of printed conductors under cyclic bending. The study proves that the bending reliability of printed conductors can be enhanced by proper design choices. This is done by minimizing the strain when the printed trace is subjected to bending. / Tiivistelmä Tässä työssä tutkitaan joustaville substraateille painettujen johdinten luotettavuutta syklisessä taivutuksessa. Aihetta lähestytään tutkimalla useiden tärkeiden suunnitteluparametrien vaikutusta painettujen johdinten elinikään dynaamisessa rasituksessa. Työssä painettiin poikkileikkausgeometrialtaan vaihtelevia testirakenteita erilaisille muovi- ja paperisubstraateille. Testinäytteet valmistettiin käyttäen kahta painotekniikkaa, silkkipainoa ja rullalta rullalle painoa, hyödyntäen kolmea erilaista hopeapastaa johtavana materiaalina. Painettujen johdinten pitkäaikaisen suorituskyvyn arvioimiseksi testinäytteet altistettiin sykliselle taivutukselle ja niiden sähköistä käyttäytymistä monitoroitiin testin aikana resistanssimittauksilla. Taivutustestin tulokset analysoitiin Weibull analyysin avulla käyttäen 20%:n kasvua resistanssissa vikakriteerinä. Tämän menetelmän lopputuloksena saatiin karakteristinen elinikä testipopulaatiolle koostuen kymmenestä yksittäisestä testinäytteestä. Vertailtaessa kaikkien valmistettujen testipopulaatioiden karakteristisiä elinikiä, havaittiin kaikilla vaihdelluilla parametreilla olevan vaikutusta painettujen johdinten luotettavuuteen. Tästä huolimatta, tutkittujen geometrioiden ja materiaalien rajoissa, substraatilla todettiin olevan suurin vaikutus painettujen johdinten pitkä-aikaiseen sähköiseen suorituskykyyn syklisessä taivutuksessa. Tämä tutkimus osoittaa, että painettujen johdinten taivutusluotettavuutta voidaan parantaa oikeilla suunnitteluvalinnoilla. Tämä voidaan toteuttaa minimoimalla venymä painetun johtimen ollessa taivutuksessa.