Design and Preparation of Stretchable Semiconductors Through Polymer Blending

A new strategy for influencing the solid-state morphology of conjugated polymers was developed through physical blending with a low molecular weight branched polyethylene (BPE). This non-toxic and low boiling point additive was blended with a high charge mobility diketopyrrolopyrrole (DPP)-based conjugated polymer and a detailed investigation of both electronic (Chapter III) and mechanical (Chapter IV) properties was performed. The new blended materials were characterized by various techniques, including X-ray diffraction, UV-Vis spectroscopy and atomic force microscopy (AFM). Interestingly, the branched additive was shown to reduce the crystallinity of the conjugated polymer, while promoting aggregation and phase separation in the solid-state. The performance of the new branched polyethylene/conjugated polymer blends was also investigated in organic field-effect transistors, which showed a stable charge mobility, independent of the blending ratio. Furthermore, by using the new BPE additive, the amount of conjugated polymer required for the fabrication of organic field-effect transistor devices was reduced down to 0.05 wt.%, without affecting charge transport, which is very promising in a large-scale fabrication of organic-field effect transistors (OFET) devices. Moreover, BPE additive acts as a plasticizer, thus drastically decreasing the crystallinity of conjugated polymers which is beneficial for the development of stretchable and flexible electronic devices. The incorporation of BPE amount to the conjugated polymer leads to an increase of the crack onset strain of polymer blends and decrease in the number of cracks, as well as their width. Our results demonstrate that the physical blending of conjugated polymer with non-toxic, low-molecular weight BPE is a promising strategy for the modification and fine-tuning of the solid-state morphology of conjugated polymers without sacrificing their charge transport properties, thus creating new opportunities for the large-scale processing of organic semiconductor

Novel solution processable dielectrics for organic and graphene transistors

In this thesis we report the development of a range of high-performance thin-film transistors utilising different solution processable organic dielectrics grown at temperatures compatible with inexpensive substrate materials such as plastic. Firstly, we study the dielectric properties and application of a novel low-k fluoropolymer dielectric, named Hyflon AD (Solvay). The orthogonal nature of the Hyflon formulation, to most conventional organic semiconductors, allows fabrication of top-gate transistors with optimised semiconductor/dielectric interface. When used as the gate dielectric in organic transistors, this transparent and highly water-repellent polymer yields high-performance devices with excellent operating stability. In the case of top-gate organic transistors, hole and electron mobility values close to or higher than 1 cm2/Vs, are obtained. These results suggest that Hyflon AD is a promising candidate for use as dielectric in organic and potentially hybrid electronics. By taking advantage of the non-reactive nature of the Hyflon AD dielectric, the p-doping process of an organic blend semiconductor using a molybdenum based organometallic complex as the molecular dopant, has also been investigated for the first time. Although the much promising properties of Hyflon AD were demonstrated, the resulting transistors need, however, to be operated at high voltages typically in the range of 50-100 V. The latter results to a high power consumption by the discrete transistors as well as the resulting integrated circuits. Therefore, reduction in the operating voltage of these devices is crucial for the implementation of the technology in portable battery-operated devices. Our approach towards the development of low-voltage organic transistors and circuits explored in this work focused on the use of self-assembled monolayer (SAM) organics as ultra-thin gate dielectrics. Only few nanometres thick (2-5 nm), these SAM dielectrics are highly insulating and yield high geometrical capacitances in the range 0.5 - 1 μF/cm2. The latter has enabled the design and development of organic transistors with operating voltages down to a few volts. Using these SAM nanodielectrics high performance transistors with ambipolar transport characteristics have also been realised and combined to form low-voltage integrated circuits for the first time. In the final part of this thesis the potential of Hyflon AD and SAM dielectrics for application in the emerging area of graphene electronics, has been explored. To this end we have employed chemical vapour deposited (CVD) graphene layers that can be processed from solution onto the surface of the organic dielectric (Hyflon AD, SAM). By careful engineering of the graphene/dielectric interface we were able to demonstrate transistors with improved operating characteristics that include; high charge carrier mobility (~1400 cm2/Vs), hysteresis free operation, negligible unintentional doping and improved reliability as compared to bare SiO2 based devices. Importantly, the use of SAM nanodielectrics has enabled the demonstration of low voltage (<|1.5| V) graphene transistors that have been processed from solution at low temperature onto flexible plastic substrates. Graphene transistors with tuneable doping characteristics were also demonstrated by taking advantage of the SAM’s flexible chemistry and more specifically the type of the chemical SAM end-group employed. Overall, the work described in this thesis represents a significant step towards flexible carbon-based electronics where large-volume and low-temperature processing are required

EXPLORATION OF NOVEL METHODS FOR THE FABRICATION AND CHARACTERIZATION OF ORGANIC FIELD-EFFECT TRANSISTORS AND EXAMINATION OF FACTORS INFLUENCING OFET PERFORMANCE

This thesis explores novel methods for fabricating organic field effect transistors (OFETs) and characterizing OFET devices. Transfer printing is a promising process for fabricating organic thin-film devices. In this work, a transfer-printing process is developed for the polymer organic semiconductor P3HT. Pre-patterned P3HT is printed onto different dielectrics such as PMMA, polystyrene and polycarbonate. The P3HT layer is spun on a smooth silicon interface made hydrophobic by treatment with octyltrichlorosilane, which functions as a release layer. This method has distinct advantages over standard OFET fabrication methods in that 1) the active layer can be pre-patterned, 2) the solvent for the P3HT need not be compatible with the target substrate, and 3) the electrical contact formed mimics the properties of top contacts but with the spatial resolution of bottom contacts. Transparent, conducting films of carbon nanotubes (CNTs) are prepared by airbrushing, and characterized optically and electronically. OFETs with CNT films as source and drain electrodes are fabricated using various patterning techniques, and the organic/CNT contact resistance is characterized. CNT films make transparent, flexible electrodes with contact resistance comparable to that found for Au bottom-contacted P3HT transistors and comparable to CNT-film bottom-contacted pentacene transistors with CNTs deposited by other less flexible methods. A transparent OFET is demonstrated using transfer printing for the assembly of an organic semiconductor (pentacene), CNT film source, drain, and gate electrodes, and polymer gate dielectric and substrate. The dependence of the conductance and mobility in pentacene OFETs on temperature, gate voltage, and source-drain electric field is studied. The data are analyzed by extending a multiple trapping and release model to account for lowering of the energy required to excite carriers into the valence band (Poole-Frenkel effect). The temperature-dependent conductivity shows activated behavior, and the activation energy is lowered roughly linearly with the square-root of electric field, as expected for the Poole-Frenkel effect. The gate voltage dependence of the activation energy is used to extract the trap density of states, in good agreement with other measurements in the literature

Dielectric Properties of ZnO-Based Nanocomposites and Their Potential Applications

Energy storage devices constitute one of the research areas in recent years. Capacitors are commonly used for the storage of electrical energy. The current research is focusing on not only the improvement in energy density but also the materials which are environment friendly. Polymer composites are known to be technically essential materials owing to their wide range of applications. Enormous research has been devoted to zinc oxide- (ZnO-) based polymer nanocomposites, due to their extraordinary dielectric properties. This review article presents a detailed study of the dielectric properties of ZnO-based nanocomposites. The dielectric constant study includes the effect of transition metals and rare earth metals as a dopant in ZnO. This review gives an insight into the mechanism responsible for the variation of dielectric constant in ZnO nanocomposites due to various factors like size of nanoparticles, thickness of the thin film, operating frequency, doping concentration, and atomic number. The observations have been summarized to convey the mechanism and structural changes involved in the ZnO nanocomposites to the researchers. The deployment of biodegradable nanocomposite materials is expected to open an innovative way for their outstanding electronic applications as storage materials

Pentacene Based Organic Electronic Devices

This thesis describes a study of pentacene-based organic electronic devices with poly(methyl methacrylate) (PMMA) and cross-linked PMMA (cPMMA) gate dielectrics. The electrical characteristics of pentacene-based organic thin-film transistors (OTFTs) using PMMA as the gate dielectric are reported. Uniform pinhole-free and crack-free films of PMMA could be obtained by spin-coating, with a lower limit to the thickness of about 150 nm. The effects of the insulator thickness and channel dimensions on the performance of the devices has been investigated. Leakage currents, which are present in many devices using polymeric gate dielectrics, were reduced by patterning the pentacene active layer. The resulting transistors exhibited minimal hysteresis in their output and transfer characteristics with an acceptable performance (a field-effect mobility of 0.33 cm2 V−1 s−1, a threshold voltage of -11 V, an on/off current ratio of 1.2X106 and a subthreshold slope of 1.5 V per decade). A bootstrapped inverter incorporating optimised pentacene OTFT structures, with PMMA as the gate dielectric, has been designed, fabricated and tested. The inverter uses capacitive coupling and bootstrapping effects, and exhibits superior performance to the normal diode-connected load inverter. The circuit has a 30 us rise time and 450 us fall time, at an operating frequency of 1 kHz and 30 V drive voltage. Pentacene-based OTFTs incorporating a PMMA gate insulator usually possess a large operating voltage, related to the thickness of the PMMA layer. A physical method, in particular ion-beam irradiation, to produce ultra-thin cross-linked layers of PMMA (33 nm) is introduced. It is demonstrated that physical cross-linking of the PMMA gate dielectric can be used to produce OTFTs with improved performance (a field-effect mobility of 1.1 cm2 V−1 s−1, a threshold voltage of -1 V, an on/off current ratio of 1.0X106 and a subthreshold slope of 220 mV per decade) and operating at low voltages, < 10 V. Low voltage memory transistors based on various charge storage elements (gold nanoparticles, ultra-thin aluminium and silver films) with cPMMA as the gate dielectric, have been investigated. Solution-processed OTFTs based on 6,13-bis(triisopropylsilylethynyl) (TIPS) pentacene with PMMA and cPMMA as the gate dielectric were also studied

Miniaturized Transistors, Volume II

In this book, we aim to address the ever-advancing progress in microelectronic device scaling. Complementary Metal-Oxide-Semiconductor (CMOS) devices continue to endure miniaturization, irrespective of the seeming physical limitations, helped by advancing fabrication techniques. We observe that miniaturization does not always refer to the latest technology node for digital transistors. Rather, by applying novel materials and device geometries, a significant reduction in the size of microelectronic devices for a broad set of applications can be achieved. The achievements made in the scaling of devices for applications beyond digital logic (e.g., high power, optoelectronics, and sensors) are taking the forefront in microelectronic miniaturization. Furthermore, all these achievements are assisted by improvements in the simulation and modeling of the involved materials and device structures. In particular, process and device technology computer-aided design (TCAD) has become indispensable in the design cycle of novel devices and technologies. It is our sincere hope that the results provided in this Special Issue prove useful to scientists and engineers who find themselves at the forefront of this rapidly evolving and broadening field. Now, more than ever, it is essential to look for solutions to find the next disrupting technologies which will allow for transistor miniaturization well beyond silicon’s physical limits and the current state-of-the-art. This requires a broad attack, including studies of novel and innovative designs as well as emerging materials which are becoming more application-specific than ever before

Enhancing the Performance of Poly(3-Hexylthiophene) Based Organic Thin-Film Transistors Using an Interface Engineering Method

An original design and photolithographic fabrication process for poly(3-hexylthiophene-2, 5-diyl) (P3HT) based organic thin-film transistors (OTFTs) is presented. The structure of the transistors was based on the bottom gate bottom contact OTFT. The fabrication process was efficient, cost-effective, and relatively straightforward to implement. Current–voltage (I-V) measurements were performed to characterize the primary electronic properties of the transistors. The measured mobility of these transistors was significantly higher than most results reported in the literature for other similar bottom gate bottom contact P3HT OTFTs. The higher mobility is explained primarily by the effectiveness of the fabrication process in keeping the interfacial layers free from contamination, as well as the proper annealing of the P3HT. An interface engineering method is investigated to further enhance the performance of the OTFTs. Three interfacial materials were used for this purpose: graphene oxide (GO), poly(oligo (ethylene glycol) methyl ether methacrylate- glycidyl methacrylate- lauryl methacrylate) (P(OEGMA-GMA-LMA)) or POGL, and a composite of GO and P(OEGMA-GMA-LMA) or GO-POGL. The OTFTs with a GO interfacial layer were observed to have a higher drain current and field-effect mobility than the OTFTs with no interfacial layer. The enhanced drain current and mobility are associated with the particular structure of the P3HT layer on the dielectric surface and the reduction in the contact resistance between the GO-covered electrodes and the P3HT. The OTFTs with a POGL interfacial layer were observed to have a smaller threshold voltage than the OTFTs with no interfacial layer. The POGL OTFTs were also observed to have much more ideal drain current saturation characteristics with very small I-V curve slope. This is explained by the deep trap states on the POGL surface and the reduction of the contact resistance at the electrode/organic semiconductor interface. The OTFTs with a GO-POGL composite layer were observed to have a higher drain current and mobility, and a smaller threshold voltage than the OTFTs without an interfacial layer, which is the optimum case for these two device parameters. The higher drain current and field-effect mobility are attributed to the larger interconnecting grains of the P3HT that is deposited onto the GO-POGL surface and the smaller interfacial tension between the GO-POGL and the P3HT. The smaller threshold voltage is attributed to the deep trap states on the GO-POGL layer and the smaller contact resistance between the GO-POGL modified electrodes and the P3HT. Furthermore, experiments that could be performed to advance this research work and enhance the performance of the OTFTs even further are proposed

Dendritic poly(3-hexylthiophene) star copolymer systems for next generation bulk heterojunction organic photovoltaic cells

Philosophiae Doctor - PhDThe continuous increase in energy consumption and decrease in fossil fuels reserves are a primary concern worldwide; especially for South Africa. Therefore, there is an urgent need for alternative energy resources that will be sustainable, and environmentally friendly in order to tackle the ecological degradation generated by the use of fossil fuels. Among many energy ‘niches’, solar energy appears to be one of the most promising and reliable for the African continent because of the constant availability of sun light. Organic conjugated polymers have been identified as suitable materials to ensure proper design and fabrication of flexible, easy to process and cost-effective solar cells. Their tendency to exhibit good semiconducting properties and their capability to absorb photons from the sunlight and convert it into electrical energy are important features that justify their use in organic photovoltaic cells. Many different polymers have been investigated as either electron donating or electron accepting materials. Among them, poly(3-hexylthiophene) is one of the best electron donor materials that have been used in organic photovoltaic cells. It is a good light absorber and its Highest Occupied Molecular Orbital (HOMO) energy level is suitable to allow electron transfer into an appropriate electron acceptor. On the other hand, the molecular ordering found in dendrimers attracted some interest in the field of photovoltaics as this feature can ensure a constant flow of charges. In this work, I hereby report for the first time, the chemical synthesis of a highly crystalline dendritic star copolymer generation 1 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene) (G1PPT-co-P3HT) with high molecular weight and investigate its application as donating material in bulk heterojunction organic photovoltaics

Gas sensors based on conducting polymers

The gas sensors fabricated by using conducting polymers such as polyaniline (PAni), polypyrrole (PPy) and poly (3,4-ethylenedioxythiophene) (PEDOT) as the active layers have been reviewed. This review discusses the sensing mechanism and configurations of the sensors. The factors that affect the performances of the gas sensors are also addressed. The disadvantages of the sensors and a brief prospect in this research field are discussed at the end of the review