This PDF file contains the front matter associated with SPIE Proceedings Volume 9944, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

Conducting polymer electrodes based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) are used to record extracellular signals from autonomous cardiac contractile cells and glioma cell cultures. The performance of these conducting polymer electrodes is compared with Au electrodes. A small-signal impedance analysis shows that in the presence of an electrolyte, both Au and polymer electrodes establish high capacitive double-layers. However, the polymer/electrolyte interfacial resistance is 3 orders of magnitude lower than the resistance of the metal/electrolyte interface. The polymer low interfacial resistance minimizes the intrinsic thermal noise and increases the system sensitivity. However, when measurements are carried out in current mode a low interfacial resistance partially acts as a short circuit of the interfacial capacitance, this affects the signal shape.

Photosynthetic Reaction Center (RC) is a transmembrane photoenzyme capable of converting absorbed photons into electron-hole pairs with almost unitary efficiency. The unique properties of this natural photoconverter attract considerable interest for its use as functional component in nanomaterials and bioelectronics devices. Implementation of RC into nanostructures or anchoring on devices’ electrode surfaces require the development of suitable chemical manipulation. Here we report our methods to embed this protein in soft nanostructures or to covalently attach it on surfaces without denaturating it or altering its chemical properties.

A key task in bioelectronics is the transduction between ionic/protonic signals and electronic signals at high fidelity. This is a considerable challenge since the two carrier types exhibit intrinsically different physics. We present our work on a new class of organic-inorganic transducing interface utilising semiconducting InAs and GaAs nanowires directly gated with a proton transporting hygroscopic polymer consisting of undoped polyethylene oxide (PEO) patterned to nanoscale dimensions by a newly developed electron-beam lithography process [1]. Remarkably, we find our undoped PEO polymer electrolyte gate dielectric [2] gives equivalent electrical performance to the more traditionally used LiClO4-doped PEO [3], with an ionic conductivity three orders of magnitude higher than previously reported for undoped PEO [4]. The observed behaviour is consistent with proton conduction in PEO. We attribute our undoped PEO-based devices’ performance to the small external surface and high surface-to-volume ratio of both the nanowire conducting channel and patterned PEO dielectric in our devices, as well as the enhanced hydration afforded by device processing and atmospheric conditions. In addition to studying the basic transducing mechanisms, we also demonstrate high-fidelity ionic to electronic conversion of a.c. signals at frequencies up to 50 Hz. Moreover, by combining complementary n- and p-type transducers we demonstrate functional hybrid ionic-electronic circuits can achieve logic (NOT operation), and with some further engineering of the nanowire contacts, potentially also amplification. Our device structures have significant potential to be scaled towards realising integrated bioelectronic circuitry. [1] D.J. Carrad et al., Nano Letters 14, 94 (2014). [2] D.J. Carrad et al., Manuscript in preparation (2016). [3] S.H. Kim et al., Advanced Materials 25, 1822 (2013). [4] S.K. Fullerton-Shirey et al., Macromolecules 42, 2142 (2009).

Organic photodetectors are able to transform plastic into intelligent surfaces making our daily life easier, smarter and more productive. The key element for a sensor is to reduce the dark current density in order to boost the limit of detection. The energetic requirements in order to select materials for ultra-high performance organic photodetectors are presented with the following experimental results: a detectivity of 3.36 × 10¹³ Jones has been achieved with an extremely low dark current density of 0.32 nA cm^-2 and a responsivity as high as 0.34 A W^-1. Flexible devices are all made at lowtemperature and with solution-processed materials. Their stability under operation is also presented.

Photosensors responsive to the short wavelength infrared (SWIR) spectra are used in a variety of applications including environmental monitoring, medical diagnosis and optical communications. However, most organic semiconductors do not absorb in the SWIR region. Here we show novel donor-acceptor polymers with narrow bandgap responsive in the SWIR region, and the polymers are processed into photodiodes with structure of ITO/PEDOT:PSS/Bulk Heterojunction (BHJ)/Al. The performance of devices with different polymer structures are compared through metrics including detectivity, quantum efficiency, response time and rectification ratio, to determine the mechanisms of charge recombination loss in charge transfer states and charge transport process. We also use different solution-processed interfacial functional layers (e.g. ZnO, MoO3, TiO2) as electrode interface structures. The results provide guideline for selecting suitable polymers and design of device structures, to enable high performance SWIR photosensor via scalable solution-processed fabrication.

Typical CMOS colour image sensors consist of Si-based photodetectors (PDs) attached with colour filter arrays (i.e., the Bayer pattern). Recent trends on the development of high resolution image sensors, however, require downsizing the pixel dimension, which inevitably results in the loss of sensitivity due to the reduction in the photon acquisition. Very recently, hybrid stacks of organic photodetectors (OPDs) on conventional CMOS technologies have been proposed as one of the promising approaches to realise highly sensitive image sensors by doubling the light detecting area in the limited pixel size. Specifically, OPDs with orthogonal photosensitivity to green light and Si-based PDs with red and blue colour filters serve as the top and bottom photo-conversion layers, respectively. In this presentation, we will introduce the recent development of high performance green light sensitive OPDs and the demonstration of colour images from hybrid CMOS image sensors proposed. OPDs consisting of small molecule organic bulk heterto-junction structures, hole/electron buffer layers, and transparent top/bottom ITO electrodes exhibited peak external quantum efficiencies of 60-65% at 550-560 nm wavelengths and full width at half maximum of ~120 nm at reverse bias of 3 V. Extremely low dark current densities in the range of 0.2-0.5 nA/cm2 at reverse bias of 3V and consequently high specific detectivities over 2×10^13 Jones were obtained from the developed OPD system. Further investigations in terms of the molecular structures of organic light absorbing materials, buffer materials, layer sequences, and even integration issues of the OPD on the CMOS will be described in detail.

Multifunctional nanoconstructs are particle-based nano-scale systems designed for the ‘smart’ delivery of therapeutic and imaging agents. The Laboratory of Nanotechnology for Precision Medicine at the Italian Institute of Technology synthesizes polymeric nanoconstructs with different sizes, ranging from a few tens of nanometers to a few microns; shapes, including spherical, cubical and discoidal; surface properties, with positive, negative, neutral coatings; and mechanical stiffness, varying from that of cells to rigid, inorganic materials, such as iron oxide. These are the 4S parameters – size, shape, surface, stiffness – which can be precisely tuned in the synthesis process enabling disease- and patient-specific designs of multifunctional nanoconstructs. In this lecture, the application of these nanoconstructs to the detection and treatment of cancer lesions and cardiovascular diseases, such as thrombosis and atherosclerosis, is discussed. The contribution of the 4S parameters in modulating nanoconstruct sequestration by the mononuclear phagocyte system, organ specific accumulation, and blood longevity is also critically presented. These polymeric nanoconstructs can be loaded with a variety of therapeutic payloads – anti-cancer molecules (docetaxel, paclitaxel, doxorubicin), anti-inflammatory molecules (curcumin, diclofenac, celecoxib) and small biologicals (peptides, siRNAs, miRNAs); and imaging agents – optical probes; Gd and iron oxide nanoparticles for MR imaging; and radio-isotopes for Nuclear Imaging.

One of the critical tasks in realising a bioelectronic interface is the transduction of ion and electron signals at high fidelity, and with appropriate speed, bandwidth and signal-to-noise ratio [1]. This is a challenging task considering ions and electrons (or holes) have drastically different physics. For example, even the lightest ions (protons) have mobilities much smaller than electrons in the best semiconductors, effective masses are quite different, and at the most basic level, ions are ‘classical’ entities and electrons ‘quantum mechanical’. These considerations dictate materials and device strategies for bioelectronic interfaces alongside practical aspects such as integration and biocompatibility [2]. In my talk I will detail these ‘differences in physics’ that are pertinent to the ion-electron transduction challenge. From this analysis, I will summarise the basic categories of device architecture that are possibilities for transducing elements and give recent examples of their realisation. Ultimately, transducing elements need to be combined to create ‘bioelectronic logic’ capable of signal processing at the interface level. In this regard, I will extend the discussion past the single element concept, and discuss our recent progress in delivering all-solids-state logic circuits based upon transducing interfaces. [1] “Ion bipolar junction transistors”, K. Tybrandt, K.C. Larsson, A. Richter-Dahlfors and M. Berggren, Proc. Natl Acad. Sci., 107, 9929 (2010). [2] “Electronic and optoelectronic materials and devices inspired by nature”, P Meredith, C.J. Bettinger, M. Irimia-Vladu, A.B. Mostert and P.E. Schwenn, Reports on Progress in Physics, 76, 034501 (2013).

We describe ongoing advances toward achieving all-organic optical sensors and a spectrometer on a chip. Two-dimensional combinatorial arrays of microcavity OLEDs (μcOLEDs) with systematically varying optical cavity lengths are fabricated on a single chip by changing the thickness of different organic and/or spacer layers sandwiched between two metal electrodes (one very thin) that form the cavity. The broad spectral range is achieved by utilizing materials that result in white OLEDs (WOLEDs) when fabricated on a standard ITO substrate. The tunable and narrower emissions from the μcOLEDs serve as excitation sources in luminescent sensors and in monitoring light absorption. For each wavelength, the light from the μcOLED is partially absorbed by a sample under study and the light emitted by an electronically excited sample, or the transmitted light is detected by a photodetector (PD). To obtain a compact monitor, an organic PD (OPD) or a perovskite-based PD is integrated with the μcOLED array. We show the potential of encompassing a broader wavelength range by using WOLED materials to fabricate the μcOLEDs. The utility of the all-organic analytical devices is demonstrated by monitoring oxygen, and bioanalytes based on oxygen detection, as well as the absorption spectra of dyes.

High-gain transistors are essential for the large-scale circuit integration, high-sensitivity sensors and signal amplification in sensing systems. Unfortunately, organic field-effect transistors show limited gain, usually of the order of tens, because of the large contact resistance and channel-length modulation. Here we show organic transistors fabricated on plastic foils enabling unipolar amplifiers with ultra-gain. The proposed approach is general and opens up new opportunities for ultra-large signal amplification in organic circuits and sensors.

Comfortable, wearable sensors and computers will enhance every person’s awareness of his or her health condition, environment, chemical pollutants, potential hazards, and information of interest. In agriculture and in the food industry there is a need for a constant control of the condition and needs of plants, animals, and farm products. Yet many of these applications depend upon the development of novel, cheap devices and sensors that are easy to implement and to integrate. Organic semiconductors as well as several inorganic materials and hybrid material systems have proven to combine a number of intriguing optical and electronic properties with simple processing methods. As it will be reviewed in this contribution, these materials are believed to find their application in printed electronic devices allowing for the development of smart disposable devices in food-, health-, and environmental monitoring, diagnostics and control, possibly integrated into arrays of sensor elements for multi-parameter detection. In this contribution we review past and recent achievements in the field. Followed by a brief introduction, we will focus on two topics being on the agenda recently: a) the use of electrolyte-gated organic field-effect transistor (EGOFET) and ion-selective membrane based sensors for in-situ sensing of ions and biological substances and b) the development of hybrid material based resistive switches and their integration into fully functional, printed hybrid crossbar sensor array structures.

A whole organic artificial synapse has been fabricated by patterning PEDOT:PSS electrodes on PDMS that are biased in frequency to yield a STP response. The timescale of the STP response is shown to be sensitive to the concentration of dopamine, DA, a neurotransmitter relevant for monitoring the development of Parkinson’s disease and potential locoregional therapies. The sensitivity of the sensor towards DA has been validated comparing signal variation in the presence of DA and its principal interfering agent, ascorbic acid, AA. The whole organic synapse is biocompatible, soft and flexible, and is attractive for implantable devices aimed to real-time monitoring of DA concentration in bodily fluids. This may open applications in chronic neurodegenerative diseases such as Parkinson’s disease.

Considering the limited physiological relevance of 2D cell culture experiments, significant effort was devoted to the development of materials that could more accurately recreate the in vivo cellular microenvironment, and support 3D cell cultures in vitro. (1) One such class of materials is conducting polymers, which are promising due to their compliant mechanical properties, compatibility with biological systems, mixed electrical and ionic conductivity, and ability to form porous structures. (2) In this work, we report the fabrication of a single component, macroporous scaffold made from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) via an ice-templating method. (3) PEDOT:PSS scaffolds offer tunable pore size, morphology and shape through facile changes in preparation conditions, and are capable of supporting 3D cell cultures due to their biocompatibility and tissue-like elasticity. Moreover, these materials are functional: they exhibit excellent electrochemical switching behavior and significantly lower impedance compared to films. Their electrochemical activity enables their use in the active channel of a state of the art diagnostic tool in the field of bioelectronics, i.e., the organic electrochemical transistor (OECT). The inclusion of cells within the porous architecture affects the impedance of the electrically-conducting polymer network and, thus, may be used as a method to quantify cell growth. The adhesion and pro-angiogenic secretions of mouse fibroblasts cultured within the scaffolds can be controlled by switching the electrochemical state of the polymer prior to cell-seeding. In summary, these smart materials hold promise not only as extracellular matrix-mimicking structures for cell culture, but also as high-performance bioelectronic tools for diagnostic and signaling applications. References [1] M. Holzwarth, P. X. Ma, Journal of Materials Chemistry, 21, 10243‐10251 (2011). [2] L. H. Jimison, J. Rivnay, R. M. Owens, in Organic Electronics, Wiley‐VCH Verlag GmbH and Co. KGaA, 27‐6 (2013). [3] A. M.-D. Wan, S. Inal, T. Williams et al. Journal of Materials Chemistry B, DOI: 10.1039/C5TB00390C (2015).

Photosensors are used for the detection of analytes in microfluidic devices. In order to detect materials with low concentrations, a sensor with high sensitivity is required. Perovskite has been studied extensively as a photoactive material in solar cells due to its wide absorption spectrum and low recombination rate of charges which also make it a suitable candidate for photosensors. In this work, the photoconductivity of the material in a thin-film resistor is studied. The resistance of the device is measured at different wavelengths and intensities. A significant change of the resistance is observed upon illumination indicating the adequacy of the device to serve as a photosensor. However, in this case, the perovskite layer must be protected with an insulating thin film to avoid undesired reactions and contacts. The perovskite film was also tested as an electrochemical photosensor. The current-voltage characteristics of the device showed a diode rectifying response both in dark and under illumination. In this case, the photo response of the device established promising results for applications in photosensors with a relatively high stability in a liquid media.

Direct measurement and stimulation of electrophysiological activity is a staple of neural and cardiac health monitoring, diagnosis and/or therapy. The ability to sensitively detect these signals can be enhanced by organic electronic materials that show mixed conduction properties (both electronic and ionic transport) in order to bridge the inherent mismatch that is prevalent between biological systems and traditional microelectronic materials/devices. Organic electrochemical transistors (OECTs) are one class of devices that utilize organic mixed conductors as the transistor channel, and have shown considerable promise as amplifying transducers due to their stability in aqueous conditions and high transconductance. These devices are fabricated in flexible, conformable form factors for in vivo recordings of epileptic activity, and for cutaneous EEG and ECG recordings in human subjects. The majority of high performance devices are based on conducting polymers such as poly(3,4-ethylenedioxythiophene) :poly(styrenesulfonate), PEDOT:PSS. By investigating PEDOT-based materials and devices, we are able to construct design rules for new formulations/materials. Introducing glycolated side chains to carefully selected semiconducting polymer backbones has enabled a new class high performance bioelectronic materials that feature high volumetric capacitance, transconductance >10mS (device dimensions ca. 10um), and steep subthreshold switching characteristics. A sub-set of these materials outperform PEDOT:PSS and shows significant promise for low power in vitro and in vivo biosensing applications.

We demonstrate the implementation of a solid state circuit/structure comprising of a high performing polymer field effect transistor (PFET) utilizing an oxide layer in conjunction with a self-assembled monolayer (SAM) as the dielectric and a bulk-heterostructure based organic photodiode as a CMOS-like pixel element for an imaging sensor. Practical usage of functional organic photon detectors requires on chip components for image capture and signal transfer as in the CMOS/CCD architecture rather than simple photodiode arrays in order to increase speed and sensitivity of the sensor. The availability of high performing PFETs with low operating voltage and photodiodes with high sensitivity provides the necessary prerequisite to implement a CMOS type image sensing device structure based on organic electronic devices. Solution processing routes in organic electronics offers relatively facile procedures to integrate these components, combined with unique features of large-area, form factor and multiple optical attributes. We utilize the inherent property of a binary mixture in a blend to phase-separate vertically and create a graded junction for effective photocurrent response. The implemented design enables photocharge generation along with on chip charge to voltage conversion with performance parameters comparable to traditional counterparts. Charge integration analysis for the passive pixel element using 2D TCAD simulations is also presented to evaluate the different processes that take place in the monolithic structure.

Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O₂ and H₂O vapor. Mass loading by O₂ was enhanced by a factor of 5 in films deposited at 250°C, possibly due to the ~200°C CuPc α→β transition which allows higher O₂ mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales < 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O₂/H₂O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O₂/H₂O molecules on gold, which is consistent with findings of other studies.

Proliferation of environmental sensors for internet of things (IoT) applications has increased the need for low-cost platforms capable of accommodating multiple sensors. Quartz crystal microbalance (QCM) crystals coated with nanometer-thin sensor films are suitable for use in high-resolution (~1 ng) selective gas sensor applications. We demonstrate a scalable array for measuring frequency response of six QCM sensors controlled by low-cost Arduino microcontrollers and a USB multiplexer. Gas pulses and data acquisition were controlled by a LabVIEW user interface. We test the sensor array by measuring the frequency shift of crystals coated with different compositions of polymer composites based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) while films are exposed to water vapor and oxygen inside a controlled environmental chamber. Our sensor array exhibits comparable performance to that of a commercial QCM system, while enabling high-throughput 6 QCM testing for under $1,000. We use deep neural network structures to process sensor response and demonstrate that the QCM array is suitable for gas sensing, environmental monitoring, and electronic-nose applications.