Manipulating nanoscale structure to control functionality in printed organic photovoltaic, transistor and bioelectronic devices.

Printed electronics is simultaneously one of the most intensely studied emerging research areas in science and technology and one of the fastest growing commercial markets in the world today. For the past decade the potential for organic electronic (OE) materials to revolutionize this printed electronics space has been widely promoted. Such conviction in the potential of these carbon-based semiconducting materials arises from their ability to be dissolved in solution, and thus the exciting possibility of simply printing a range of multifunctional devices onto flexible substrates at high speeds for very low cost using standard roll-to-roll printing techniques. However, the transition from promising laboratory innovations to large scale prototypes requires precise control of nanoscale material and device structure across large areas during printing fabrication. Maintaining this nanoscale material control during printing presents a significant new challenge that demands the coupling of OE materials and devices with clever nanoscience fabrication approaches that are adapted to the limited thermodynamic levers available. In this review we present an update on the strategies and capabilities that are required in order to manipulate the nanoscale structure of large area printed organic photovoltaic (OPV), transistor and bioelectronics devices in order to control their device functionality. This discussion covers a range of efforts to manipulate the electroactive ink materials and their nanostructured assembly into devices, and also device processing strategies to tune the nanoscale material properties and assembly routes through printing fabrication. The review finishes by highlighting progress in printed OE devices that provide a feedback loop between laboratory nanoscience innovations and their feasibility in adapting to large scale printing fabrication. The ability to control material properties on the nanoscale whilst simultaneously printing functional devices on the square metre scale is prompting innovative developments in the targeted nanoscience required for OPV, transistor and biofunctional devices

Photolithographic micropatterning of organic, flexible biomaterials and its applications

A current trend in biodevices has involved a shift from traditional rigid platforms to flexible and stretchable formats. These flexible devices are expected to have a significant impact on future healthcare, disease diagnostics and therapeutics. However, the fabrication of such flexible devices has been limited by the choice of materials. Biomimetic composites of naturally derived and synthetic polymers provide exciting opportunities to develop mechanically flexible, physiologically compliant, and degradable bioelectronic systems. Advantages include the ability to provide conformal contact at non-planar biointerfaces, being able to be degraded at controllable rate, and invoking minimal reactions within the body. These factors present great potential as implantable devices for in-vivo applications, while also addressing concerns with “electronic waste” by being intrinsically degradable. In this work, we present a combination of photo-crosslinkable silk proteins and conductive polymers to precisely fabricate flexible devices and cell culture substrate. A facile and scalable photolithography is applied to fabricate flexible substrates with conductive and non- conductive micropatterns which show tuneable electrical and mechanical properties. We also demonstrate an approach to engineer flexibility in materials through the creation of patterned defects inspired from Kirigami- the Japanese art of paper cutting. Mechanically flexible, free- standing, optically transparent, large-area biomaterial sheets with precisely defined and computationally designed microscale cuts can be formed using a single-step photolithographic process. As composites with conducting polymers, flexible, intrinsically electroactive sheets can be formed. Through this work, the possibility of making next- generation, fully organic, flexible bioelectronics is explored.https://scholarscompass.vcu.edu/gradposters/1099/thumbnail.jp

Functionalization Strategies of PEDOT and PEDOT:PSS Films for Organic Bioelectronics Applications

Organic bioelectronics involves the connection of organic semiconductors with living organisms, organs, tissues, cells, membranes, proteins, and even small molecules. In recent years, this field has received great interest due to the development of all kinds of devices architectures, enabling the detection of several relevant biomarkers, the stimulation and sensing of cells and tissues, and the recording of electrophysiological signals, among others. In this review, we discuss recent func-tionalization approaches for PEDOT and PEDOT:PSS films with the aim of integrating biomolecules for the fabrication of bioelectronics platforms. As the choice of the strategy is determined by the conducting polymer synthesis method, initially PEDOT and PEDOT:PSS films preparation methods are presented. Later, a wide variety of PEDOT functionalization approaches are discussed, together with bioconjugation techniques to develop efficient organic-biological interfaces. Finally, and by making use of these approaches, the fabrication of different platforms towards organic bioelectronics devices is reviewed.Fil: Fenoy, Gonzalo Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Knoll, Wolfgang. Ait Austrian Institute of Technology Gmbh; Austria. Danube Private University; AustriaFil: Marmisollé, Waldemar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Chemical and biological sensors based on van der Waals heterostructures of graphene and carbon nanomembrane

In this thesis, single-layer graphene (SLG)-based field-effect devices were built to realize two different sensors: a pH sensor and a sensor measuring the concentration of the chemokine CXCL8 in clinical samples. CXCL8 is a signal protein that has various promising new applications in the field of disease diagnostics.20 For building these devices, a recently proposed new functionalization approach for graphene was employed.78 The approach is based on the assembly of an all-carbon van der Waals (vdW) heterostructure of carbon nanomembrane (CNM) and SLG. The effect of different substrates including SiO2, poly(ethylene 2,6-naphthalate) (PEN) and SiC and different types of SLG including graphene grown by chemical vapor deposition (CVD), epitaxial graphene, and nanoporous graphene (NPSLG) on the sensor response was investigated. Devices of increasing complexity were designed and investigated. At first, devices for measurements in vacuum. As a next step, devices for measurements of the pH value, and as final step the devices for biosensing. The fabrication of devices included their successive optimization based on transport measurements, electrical impedance spectroscopy (EIS) measurements, and surface sensitive characterization techniques. The device concept was the solution-gated field-effect transistor (SGFET),33 which has promising applications for point-of-care devices247 and lab-onchip technology

Contribution of resonance energy transfer to the luminescence quenching of upconversion nanoparticles with graphene oxide

Upconversion nanoparticles (UCNP) are increasingly used due to their advantages over conventional fluorophores, and their use as resonance energy transfer (RET) donors has permitted their application as biosensors when they are combined with appropriate RET acceptors such as graphene oxide (GO). However, there is a lack of knowledge about the design and influence that GO composition produces over the quenching of these nanoparticles that in turn will define their performance as sensors. In this work, we have analysed the total quenching efficiency, as well as the actual values corresponding to the RET process between UCNPs and GO sheets with three different chemical compositions. Our findings indicate that excitation and emission absorption by GO sheets are the major contributor to the observed luminescence quenching in these systems. This challenges the general assumption that UCNPs luminescence deactivation by GO is caused by RET. Furthermore, RET efficiency has been theoretically calculated by means of a semiclassical model considering the different nonradiative energy transfer rates from each Er3+ ion to the GO thin film. These theoretical results highlight the relevance of the relative positions of the Er3+ ions inside the UCNP with respect to the GO sheet in order to explain the RET-induced efficiency measurements

Biocompatible chitosan-functionalized upconverting nanocomposites

Simultaneous integration of photon emission and biocompatibility into nanoparticles is an interesting strategy to develop applications of advanced optical materials. In this work, we present the synthesis of biocompatible optical nanocomposites from the combination of near-infrared luminescent lanthanide nanoparticles and water-soluble chitosan. NaYF4:Yb,Er upconverting nanocrystal guests and water-soluble chitosan hosts are prepared and integrated together into biofunctional optical composites. The control of aqueous dissolution, gelation, assembly, and drying of NaYF4:Yb,Er nanocolloids and chitosan liquids allowed us to design novel optical structures of spongelike aerogels and beadlike microspheres. Well-defined shape and near-infrared response lead upconverting nanocrystals to serve as photon converters to couple with plasmonic gold (Au) nanoparticles. Biocompatible chitosan-stabilized Au/NaYF4:Yb,Er nanocomposites are prepared to show their potential use in biomedicine as we find them exhibiting a half-maximal effective concentration (EC50) of 0.58 mg mL–1 for chitosan-stabilized Au/NaYF4:Yb,Er nanorods versus 0.24 mg mL–1 for chitosan-stabilized NaYF4:Yb,Er after 24 h. As a result of their low cytotoxicity and upconverting response, these novel materials hold promise to be interesting for biomedicine, analytical sensing, and other applications