Novel materials for direct X-ray detectors based on semiconducting organic polymers

Conventional inorganic materials for x-ray radiation sensors suffer from several drawbacks, including their inability to cover large curved areas, me- chanical sti ffness, lack of tissue-equivalence and toxicity. Semiconducting organic polymers represent an alternative and have been employed as di- rect photoconversion material in organic diodes. In contrast to inorganic detector materials, polymers allow low-cost and large area fabrication by sol- vent based methods. In addition their processing is compliant with fexible low-temperature substrates. Flexible and large-area detectors are needed for dosimetry in medical radiotherapy and security applications. The objective of my thesis is to achieve optimized organic polymer diodes for fexible, di- rect x-ray detectors. To this end polymer diodes based on two different semi- conducting polymers, polyvinylcarbazole (PVK) and poly(9,9-dioctyluorene) (PFO) have been fabricated. The diodes show state-of-the-art rectifying be- haviour and hole transport mobilities comparable to reference materials. In order to improve the X-ray stopping power, high-Z nanoparticle Bi2O3 or WO3 where added to realize a polymer-nanoparticle composite with opti- mized properities. X-ray detector characterization resulted in sensitivties of up to 14 uC/Gy/cm2 for PVK when diodes were operated in reverse. Addition of nanoparticles could further improve the performance and a maximum sensitivy of 19 uC/Gy/cm2 was obtained for the PFO diodes. Compared to the pure PFO diode this corresponds to a five-fold increase and thus highlights the potentiality of nanoparticles for polymer detector design. In- terestingly the pure polymer diodes showed an order of magnitude increase in sensitivity when operated in forward regime. The increase was attributed to a different detection mechanism based on the modulation of the diodes conductivity.

Stabilizzazione del Blu di Prussia con film politiofenici depositati per via elettrochimica

Hydrogen peroxide (H2O2) is a powerful oxidant which is commonly used in a wide range of applications in the industrial field. Several methods for the quantification of H2O2 have been developed. Among them, electrochemical methods exploit the ability of some hexacyanoferrates (such as Prussian Blue) to detect H2O2 at potentials close to 0.0 V (vs. SCE) avoiding the occurrence of secondary reactions, which are likely to run at large overpotentials. This electrocatalytic behaviour makes hexacyanoferrates excellent redox mediators. When deposited in the form of thin films on the electrode surfaces, they can be employed in the fabrication of sensors and biosensors, normally operated in solutions at pH values close to physiological ones. As hexacyanoferrates show limited stability in not strongly acidic solutions, it is necessary to improve the configuration of the modified electrodes to increase the stability of the films. In this thesis work, organic conducting polymers were used to fabricate composite films with Prussian Blue (PB) to be electro-deposited on Pt surfaces, in order to increase their pH stability. Different electrode configurations and different methods of synthesis of both components were tested, and for each one the achievement of a possible increase in the operational stability of Prussian Blue was verified. Good results were obtained for the polymer 3,3''-didodecyl-2,2':5',2''-terthiophene (poly(3,3''-DDTT)), whose presence created a favourable microenvironment for the electrodeposition of Prussian Blue. The electrochemical behaviour of the modified electrodes was studied in both aqueous and organic solutions. Poly(3,3''-DDTT) showed no response in aqueous solution in the potential range where PB is electroactive, thus in buffered aqueous solution is was possible to characterize the composite material, focusing only on the redox behaviour of PB. A combined effect of anion and cation of the supporting electrolyte was noticed. The response of Pt electrodes modified with films of the PB /poly(3,3''-DDTT) composite was evaluated for the determination of H2O2. The performance of such films was found better than that of the PB alone. It can be concluded that poly(3,3''-DDTT) plays a key role in the stabilization of Prussian Blue causing also a wider linearity range for the electrocatalytic response to H2O2.

PEDOT:PSS thin films: Applications in Bioelectronics

Owing to their capability of merging the properties of metals and conventional polymers, Conducting Polymers (CPs) are a unique class of carbon-based materials capable of conducting electrical current. A conjugated backbone is the hallmark of CPs, which can readily undergo reversible doping to different extents, thus achieving a wide range of electrical conductivities, while maintaining mechanical flexibility, transparency and high thermal stability. Thanks to these inherent versatility and attracting properties, from their discovery CPs have experienced incessant widespread in a great plethora of research fields, ranging from energy storage to healthcare, also encouraging the spring and growth of new scientific areas with highly innovative content. Nowadays, Bioelectronics stands out as one of the most promising research fields, dealing with the mutual interplay between biology and electronics. Among CPs, the polyelectrolyte complex poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), especially in the form of thin films, has been emphasized as ideal platform for bioelectronic applications. Indeed, in the last two decades PEDOT:PSS has played a key role in the sensing of bioanalytes and living cells interfacing and monitoring. In the present work, development and characterization of two kinds of PEDOT:PSS-based devices for applications in Bioelectronics are discussed in detail. In particular, a low-cost amperometric sensor for the selective detection of Dopamine in a ternary mixture was optimized, taking advantage of the electrocatalytic and antifouling properties that render PEDOT:PSS thin films appealing tools for electrochemical sensing of bioanalytes. Moreover, the potentialities of this material to interact with live cells were explored through the fabrication of a microfluidic trapping device for electrical monitoring of 3D spheroids using an impedance-based approach.

Development of wearable electrochemical sensors for the determination of biological analytes

Wearable biosensors are attracting interest due to their potential to provide continuous, real-time physiological information via dynamic, non-invasive measurements of biochemical markers in biofluids, such as interstitial fluid (ISF). One notable example of their applications is for glycemic monitoring in diabetic patients, which is typically carried out either by direct measurement of blood glucose via finger pricking or by wearable sensors that can continuously monitor glucose in ISF by sampling it from below the skin with a microneedle. In this context, the development of a new and minimally invasive multisensing tattoo-based platform for the monitoring of glucose and other analytes in ISF extracted through reverse iontophoresis in proposed by the GLUCOMFORT project. This elaborate describes the in-vitro development of flexible electrochemical sensors based on inkjet-printed PEDOT:PSS and metal inks that are capable of determining glucose and chloride at biologically relevant concentrations, making them good candidates for application in the GLUCOMFORT platform. In order to make PEDOT:PSS sensitive to glucose at micromolar concentrations, a biocompatible functionalization based on immobilized glucose oxidase and electrodeposited platinum was developed. This functionalization was successfully applied to bulk and flexible amperometric devices, the design of which was also optimized. Using the same strategy, flexible organic electrochemical transistors (OECTs) for glucose sensing were also made and successfully tested. For the sensing of chloride ions, an organic charge-modulated field-effect transistor (OCMFET) featuring a silver/silver chloride modified floating gate electrode was developed and tested.

Charge accumulation and transport in degenerately doped semiconducting polymers with mixed ionic and electronic conductivity

This thesis is part of the fields of Material Physics and Organic Electronics and aims to determine the charge carrier density and mobility in the hydrated conducting polymer–polyelectrolyte blend PEDOT:PSS. This kind of material combines electronic semiconductor functionality with selective ionic transport, biocompatibility and electrochemical stability in water. This advantageous material properties combination makes PEDOT:PSS a unique material to build organic electrochemical transistors (OECTs), which have relevant application as amplifying transducers for bioelectronic signals. In order to measure charge carrier density and mobility, an innovative 4-wire, contact independent characterization technique was introduced, the electrolyte-gated van der Pauw (EgVDP) method, which was combined with electrochemical impedance spectroscopy. The technique was applied to macroscopic thin film samples and micro-structured PEDOT:PSS thin film devices fabricated using photolithography. The EgVDP method revealed to be effective for the measurements of holes’ mobility in hydrated PEDOT:PSS thin films, which resulted to be <μ>=(0.67±0.02) cm^2/(V*s). By comparing this result with 2-point-probe measurements, we found that contact resistance effects led to a mobility overestimation in the latter. Ion accumulation at the drain contact creates a gate-dependent potential barrier and is discussed as a probable reason for the overestimation in 2-point-probe measurements. The measured charge transport properties of PEDOT:PSS were analyzed in the framework of an extended drift-diffusion model. The extended model fits well also to the non-linear response in the transport characterization and results suggest a Gaussian DOS for PEDOT:PSS. The PEDOT:PSS-electrolyte interface capacitance resulted to be voltage-independent, confirming the hypothesis of its morphological origin, related to the separation between the electronic (PEDOT) and ionic (PSS) phases in the blend.