Minimally invasive power sources for implantable electronics.

As implantable medical electronics (IMEs) developed for healthcare monitoring and biomedical therapy are extensively explored and deployed clinically, the demand for non-invasive implantable biomedical electronics is rapidly surging. Current rigid and bulky implantable microelectronic power sources are prone to immune rejection and incision, or cannot provide enough energy for long-term use, which greatly limits the development of miniaturized implantable medical devices. Herein, a comprehensive review of the historical development of IMEs and the applicable miniaturized power sources along with their advantages and limitations is given. Despite recent advances in microfabrication techniques, biocompatible materials have facilitated the development of IMEs system toward non-invasive, ultra-flexible, bioresorbable, wireless and multifunctional, progress in the development of minimally invasive power sources in implantable systems has remained limited. Here three promising minimally invasive power sources summarized, including energy storage devices (biodegradable primary batteries, rechargeable batteries and supercapacitors), human body energy harvesters (nanogenerators and biofuel cells) and wireless power transfer (far-field radiofrequency radiation, near-field wireless power transfer, ultrasonic and photovoltaic power transfer). The energy storage and energy harvesting mechanism, configurational design, material selection, output power and in vivo applications are also discussed. It is expected to give a comprehensive understanding of the minimally invasive power sources driven IMEs system for painless health monitoring and biomedical therapy with long-term stable functions.

Colour-sensitive conjugated polymer inkjet-printed pixelated artificial retina model studied via a bio-hybrid photovoltaic device.

In recent years, organic electronic materials have been shown to be a promising tool, even transplanted in vivo, for transducing light stimuli to non-functioning retinas. Here we developed a bio-hybrid optoelectronic device consisting of patterned organic polymer semiconductors interfaced with an electrolyte solution in a closed sandwich architecture in order to study the photo-response of photosensitive semiconducting layers or patterns in an environment imitating biological extracellular fluids. We demonstrate an artificial retina model composed of on an array of 42,100 pixels made of three different conjugated polymers via inkjet printing with 110 pixels/mm2 packing density. Photo-sensing through three-colour pixelation allows to resolve incoming light spectrally and spatially. The compact colour sensitive optoelectronic device represents an easy-to-handle photosensitive platform for the study of the photo response of artificial retina systems.

Low-Cost Catalyst Ink for Simple Patterning and Growth of High-Quality Single- and Double-Walled Carbon Nanotubes.

Research into carbon nanotubes (CNTs) has been a hot topic for almost 3 decades, and it is now that we are beginning to observe the impact of advanced applictions of this nanomaterial in areas such as electronics. Currently, in order to mass produce CNT devices, either large-scale synthesis, followed by numerous energy-intensive processing steps or photolithography processes, including several sputter-deposition steps, are required to pattern this material to fabricate functional devices. In the work reported here, through the utilization of a universal catalyst precursor (cyclopentadienyl iron dicarbonyl dimer) and the optimization of solution parameters, patterned high-quality vertically aligned arrays of single- and few-walled CNTs have been synthesized via various inexpensive, commercially scalable methods such as inkjet printing, stamp printing, spray painting, and even handwriting. The two-step process of precursor printing, followed immediately by CNT growth, results in CNTs with a Raman ID/IG ratio of 0.073, demonstrating very high-quality nanotubes. This process eliminates time-consuming and costly CNT post processing techniques or the deposition of numerous substrate barrier and catalyst layers to achieve device manufacturing. As a result, this method has the potential to provide a route for the large-scale synthesis of high-quality single- and few-walled CNTs that can be applied in industrial settings.

Water-Transferred, Inkjet-Printed Supercapacitors toward Conformal and Epidermal Energy Storage.

Rapid growth of the internet of things and health monitoring systems have stimulated the development of flexible, wearable, and conformal embedded electronics with the unprecedented need for energy storage systems fully adaptable to diverse form factors. Conventional fabrication methods, such as photolithography for electronics and electrode winding/stacking for energy storage systems, struggle as fabrication strategies to produce devices with three-dimensional, stretchable, and conformal form factors. In this study, we demonstrate the fabrication of supercapacitors on 3D objects through inkjet and water-transfer printing. The devices are initially printed on a water-soluble substrate, which is then placed on the surface of water. Once the substrate is dissolved, the level of water is lowered until the devices are transferred on to the submerged 3D object. As a proof of concept, planar supercapacitors constituted of a silver nanoparticle-based current collector, nickel(II) oxide (NiO) nanoparticle-based active electrodes, and ultraviolet-cured triacrylate polymer-based solid-state electrolyte were used as model materials. The conformal supercapacitors showed a maximum areal capacitance of 87.2 mF·cm-2 at a voltage window of 0-1.5 V. Moreover, the concept of water transfer was further explored with a particular focus on wearable applications by transferring the supercapacitors onto the skin of a human subject to realize epidermal energy storage. This new class of conformal electrochemical energy storage offers a new alternative approach toward monolithically integrated/object-tailored energy storage systems that are essential for complex-shaped devices for internet of things and flexible/on-skin electronic applications.

Laser Patterned Polymer/Carbon Nanotubes Composite Electrodes for Flexible Silicon Nanowire Transistors.

Fabrication techniques such as laser patterning offer excellent potential for low cost and large area device fabrication. Conductive polymers can be used to replace expensive metallic inks such as silver and gold nanoparticles for printing technology. Electrical conductivity of the polymers can be improved by blending with carbon nanotubes. In this work, formulations of acid functionalized multiwalled carbon nanotubes (f-MWCNTs) and poly(ethylenedioxythiophene) [PEDOT]:polystyrene sulphonate [PSS] were processed, and thin films were prepared on plastic substrates. Conductivity of PEDOT:PSS increased almost four orders of magnitude after adding f-MWCNTs. Work function of PEDOT:PSS/f-MWCNTs films was ∼0.5 eV higher as compared to the work function of pure PEDOT:PSS films, determined by Kelvin probe method. Field-effect transistors source-drain electrodes were prepared on PET plastic substrates where PEDOT:PSS/f-MWCNTs were patterned using laser ablation at 44 mJ/pulse energy to define 36 µm electrode separation. Silicon nanowires were deposited using dielectrophoresis alignment technique to bridge laser patterned electrodes. Top-gated nanowire field effect transistors were completed by depositing parylene C as polymer gate dielectric and gold as the top-gate electrode. Transistor characteristics showed p-type conduction with excellent gate electrode coupling, with an ON/OFF ratio of ∼200. Thereby, we demonstrate the feasibility of using high workfunction, printable PEDOT:PSS/f-MWCNTs composite inks for laser patterned source/drain electrodes for nanowire transistors on flexible substrates.

Photonic Curing of Low-Cost Aqueous Silver Flake Inks for Printed Conductors with Increased Yield.

Printing of highly conductive tracks at low cost is of primary importance for the emerging field of flexible, plastic, and large-area electronics. Commonly, this is achieved by printing of metallic conductive inks, often based on Ag or Cu nanoparticles dispersed in organic solvents. The solvents, which must be safely removed, have particular storage and handling requirements, thus increasing the process costs. By using water-based inks containing micron-sized silver flakes, both material and process costs can be reduced, making these inks attractive for industrial applications. However, the sintering of flake inks requires higher temperatures than nano-sized inks owing to the particles' smaller surface area-to-volume ratio, meaning that when cured thermally the conductivity of many flake inks is lower than nanoparticle alternatives. This problem can be addressed by the application of visible light photonic curing; however, the substrate must be protected and so process parameters must be defined for each material/substrate combination. Here, we report results of a large-scale trial of photonic curing of aqueous flake silver inks on poly(ethylene terephthalate) substrates in an industrial setting. The resistivity of printed patterns after an optimized photocuring regime matched those reported for typical nanoparticle inks; on the order of 100 µΩ cm depending on substrate and geometry. Scanning electron microscopy revealed evidence for structural changes within the printed films consistent with localized melting and necking between adjacent particles, leading to an improved percolation network. Furthermore, in the large-scale industrial trial employing screen-printed silver lines, the manufacturing yield of conductive lines was increased from 44% untreated to 80% after photocuring and reached 100% when photocuring was combined with thermal curing. We believe this to be the first reported observation of an increase in the yield of printed electronic structures following photocuring. We propose a crack-healing mechanism to explain these increases in yield and conductivity. We further report on the effects of the photonic curing on the mechanical bending stability of the printed conductors and discuss their suitability for wearable applications.

Flow-assisted Dielectrophoresis: A Low Cost Method for the Fabrication of High Performance Solution-processable Nanowire Devices.

Flow-assisted dielectrophoresis (DEP) is an efficient self-assembly method for the controllable and reproducible positioning, alignment, and selection of nanowires. DEP is used for nanowire analysis, characterization, and for solution-based fabrication of semiconducting devices. The method works by applying an alternating electric field between metallic electrodes. The nanowire formulation is then dropped onto the electrodes which are on an inclined surface to create a flow of the formulation using gravity. The nanowires then align along the gradient of the electric field and in the direction of the liquid flow. The frequency of the field can be adjusted to select nanowires with superior conductivity and lower trap density. In this work, flow-assisted DEP is used to create nanowire field effect transistors. Flow-assisted DEP has several advantages: it allows selection of nanowire electrical properties; control of nanowire length; placement of nanowires in specific areas; control of orientation of nanowires; and control of nanowire density in the device. The technique can be expanded to many other applications such as gas sensors and microwave switches. The technique is efficient, quick, reproducible, and it uses a minimal amount of dilute solution making it ideal for the testing of novel nanomaterials. Wafer scale assembly of nanowire devices can also be achieved using this technique, allowing large numbers of samples for testing and large-area electronic applications.

Effects of ambient humidity on the optimum annealing time of mixed-halide Perovskite solar cells.

Mixed halide Perovskite solar cells (PSCs) are commonly produced by depositing PbCl2 and CH3NH3I from a common solvent followed by thermal annealing, which in an up-scaled manufacturing process is likely to take place under ambient conditions. However, it has been reported that, similar to the effects of thermal annealing, ambient humidity also affects the crystallisation behaviour and subsequent growth of the Perovskite films. This implies that both of these factors must be accounted for in solar cell production. In this work, we report for the first time the correlation between the annealing time, relative humidity (RH) and device performance for inverted, mixed halide CH3NH3PbI(3-x)Cl x PSCs with active area ≈1 cm2. We find a trade-off between ambient humidity and the required annealing time to produce efficient solar cells, with low humidities needing longer annealing times and vice-versa. At around 20% RH, device performance weakly depends on annealing time, but at higher (30%-40% RH) or lower (0%-15% RH) humidities it is very sensitive. Processing in humid environments is shown to lead to the growth of both larger Perovskite grains and larger voids; similar to the effect of thermal annealing, which also leads to grain growth. Therefore, samples which are annealed for too long under high humidity show loss of performance due to low open circuit voltage caused by an increased number of shunt paths. Based on these results it is clear that humidity and annealing time are closely interrelated and both are important factors affecting the performance of PSCs. The findings of this work open a route for reduced annealing times to be employed by control of humidity; critical in roll-to-roll manufacture where low manufacturing time is preferred for cost reductions.

Rapid determination of nanowire electrical properties using a dielectrophoresis-well based system.

The use of high quality semiconducting nanomaterials for advanced device applications has been hampered by the unavoidable variability in the growth of one-dimensional (1D) nanomaterials such as nanowires (NWs) and nanotubes, resulting in highly variable electrical properties across the population. Therefore, assessment of the quality of nanomaterials is vital for the fabrication of high-performance and reliable electronic devices. The controllable selection of high quality NWs has been recently demonstrated using a dielectrophoretic (DEP) NW assembly method; however, no convenient, rapid method has been adopted for the characterization of nanomaterial semiconducting properties. In this study, we solve this challenge with a low-cost, industrially scalable method for the rapid analysis of the electrical properties of inorganic single crystalline NWs, by identifying key features in the DEP frequency response spectrum (1 kHz - 20 MHz). NWs dispersed in anisole were characterized using a three-dimensional DEP chip (3DEP) in 60 seconds, and the resultant spectrum demonstrated a sharp change in NW response to DEP signal in 1 MHz - 20 MHz frequency rage. The 3DEP analysis, confirmed by field-effect transistor (FET) data, indicates that NWs with higher quality are collected at high DEP signal frequency range such as above 10 MHz. These results show that platforms such as the 3DEP, can be used for the characterization of rod-shaped nanoscale particles where the dipole moment is sufficiently large. It also shows that the 3DEP can be used to assess heterogeneous nanoparticle mixtures and identify nanomaterials with superior conductivity properties. The proposed methodology can be applied to any type of 1D nanomaterials. The 3DEP analysis coupled with dielectrophoretic assembly for the deposition of NWs at selected signal frequencies, leads to a reproducible fabrication of high quality NW FET devices.

Spray printing of organic semiconducting single crystals.

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by combining the advantages of antisolvent crystallization and solution shearing. The crystals' size, shape and orientation are controlled by the sheer force generated by the spray droplets' impact onto the antisolvent's surface. This method demonstrates the feasibility of a spray-on single-crystal organic electronics.

Precise Characterisation of Molecular Orientation in a Single Crystal Field-Effect Transistor Using Polarised Raman Spectroscopy.

Charge transport in organic semiconductors is strongly dependent on the molecular orientation and packing, such that manipulation of this molecular packing is a proven technique for enhancing the charge mobility in organic transistors. However, quantitative measurements of molecular orientation in micrometre-scale structures are experimentally challenging. Several research groups have suggested polarised Raman spectroscopy as a suitable technique for these measurements and have been able to partially characterise molecular orientations using one or two orientation parameters. Here we demonstrate a new approach that allows quantitative measurements of molecular orientations in terms of three parameters, offering the complete characterisation of a three-dimensional orientation. We apply this new method to organic semiconductor molecules in a single crystal field-effect transistor in order to correlate the measured orientation with charge carrier mobility measurements. This approach offers the opportunity for micrometre resolution (diffraction limited) spatial mapping of molecular orientation using bench-top apparatus, enabling a rational approach towards controlling this orientation to achieve optimum device performance.

Simultaneous Tunable Selection and Self-Assembly of Si Nanowires from Heterogeneous Feedstock.

Semiconducting nanowires (NWs) are becoming essential nanobuilding blocks for advanced devices from sensors to energy harvesters, however their full technology penetration requires large scale materials synthesis together with efficient NW assembly methods. We demonstrate a scalable one-step solution process for the direct selection, collection, and ordered assembly of silicon NWs with desired electrical properties from a poly disperse collection of NWs obtained from a supercritical fluid-liquid-solid growth process. Dielectrophoresis (DEP) combined with impedance spectroscopy provides a selection mechanism at high signal frequencies (>500 kHz) to isolate NWs with the highest conductivity and lowest defect density. The technique allows simultaneous control of five key parameters in NW assembly: selection of electrical properties, control of NW length, placement in predefined electrode areas, highly preferential orientation along the device channel, and control of NWs deposition density from few to hundreds per device. Direct correlation between DEP signal frequency and deposited NWs conductivity is confirmed by field-effect transistor and conducting AFM data. Fabricated NW transistor devices demonstrate excellent performance with up to 1.6 mA current, 10(6)-10(7) on/off ratio and hole mobility of 50 cm(2) V(-1) s(-1).

Interface Passivation and Trap Reduction via a Solution-Based Method for Near-Zero Hysteresis Nanowire Field-Effect Transistors.

In this letter, we demonstrate a solution-based method for a one-step deposition and surface passivation of the as-grown silicon nanowires (Si NWs). Using N,N-dimethylformamide (DMF) as a mild oxidizing agent, the NWs' surface traps density was reduced by over 2 orders of magnitude from 1×10(13) cm(-2) in pristine NWs to 3.7×10(10) cm(-2) in DMF-treated NWs, leading to a dramatic hysteresis reduction in NW field-effect transistors (FETs) from up to 32 V to a near-zero hysteresis. The change of the polyphenylsilane NW shell stoichiometric composition was confirmed by X-ray photoelectron spectroscopy analysis showing a 35% increase in fully oxidized Si4+ species for DMF-treated NWs compared to dry NW powder. Additionally, a shell oxidation effect induced by DMF resulted is a more stable NW FET performance with steady transistor currents and only 1.5 V hysteresis after 1000 h of air exposure.

Direct detection of 6 MV x-rays from a medical linear accelerator using a semiconducting polymer diode.

Recently, a new family of low-cost x-radiation detectors have been developed, based on semiconducting polymer diodes, which are easy to process, mechanically flexible, relatively inexpensive, and able to cover large areas. To test their potential for radiotherapy applications such as beam monitors or dosimeters, as an alternative to the use of solid-state inorganic detectors, we present the direct detection of 6 MV x-rays from a medical linear accelerator using a thick film, semiconducting polymer detector. The diode was subjected to 4 ms pulses of 6 MV x-rays at a rate of 60 Hz, and produces a linear increase in photocurrent with increasing dose rate (from 16.7 to 66.7 mGy s(-1)). The sensitivity of the diode was found to range from 13 to 20 nC mGy(-1) cm(-3), for operating voltages from -50 to -150 V, respectively. The diode response was found to be stable after exposure to doses up to 15 Gy. Testing beyond this dose range was not carried out. Theoretical calculations show that the addition of heavy metallic nanoparticles to polymer films, even at low volume fractions, increases the x-ray sensitivity of the polymer film/nanoparticle composite so that it exceeds that for silicon over a wide range of x-ray energies. The possibility of detecting x-rays with energies relevant to medical oncology applications opens up the potential for these polymer detectors to be used in detection and imaging applications using medical x-ray beams.

The incorporation of mono- and bi-functionalized multiwall carbon nanotubes in organic photovoltaic cells.

We have successfully prepared mono- and bi-functionalized multiwall carbon nanotubes (MWCNT) with thiophene, amine and thiophene-amine groups. The dispersion of nanotubes has been enhanced and stable optimized dispersions in organic solvents were obtained. These functionalized nanotubes have been successfully incorporated into bulk heterojunction (BHJ) organic photovoltaic (OPV) cells with a poly (3-hexyl thiophene) (P3HT) and [6, 6]-phenyl-C(61)-butyric acid methyl ester (PCBM) photoactive blended layer. The incorporation of MWCNT with different functional groups, in the active layer, results in different cell performance with respect to a reference cell. A maximum power conversion efficiency of 2.5% is achieved with the inclusion of thiophene functionalized nanotubes. This improvement in the device performance is attributed to an extension of the exciton dissociation volume and charge transport properties through the nanotube percolation network in P3HT/CNT, PCBM/CNT or both phases. This is believed to be due to more efficient dispersion of the functionalized nanotubes within the photoactive composite layer.

Achieving a stable time response in polymeric radiation sensors under charge injection by X-rays.

Existing inorganic materials for radiation sensors suffer from several drawbacks, including their inability to cover large curved areas, lack of tissue-equivalence, toxicity, and mechanical inflexibility. As an alternative to inorganics, poly(triarylamine) (PTAA) diodes have been evaluated for their suitability for detecting radiation via the direct creation of X-ray induced photocurrents. A single layer of PTAA is deposited on indium tin oxide (ITO) substrates, with top electrodes selected from Al, Au, Ni, and Pd. The choice of metal electrode has a pronounced effect on the performance of the device; there is a direct correlation between the diode rectification factor and the metal-PTAA barrier height. A diode with an Al contact shows the highest quality of rectifying junction, and it produces a high X-ray photocurrent (several nA) that is stable during continuous exposure to 50 kV Mo Kalpha X-radiation over long time scales, combined with a high signal-to-noise ratio with fast response times of less than 0.25 s. Diodes with a low band gap, 'Ohmic' contact, such as ITO/PTAA/Au, show a slow transient response. This result can be explained by the build-up of space charge at the metal-PTAA interface, caused by a high level of charge injection due to X-ray-induced carriers. These data provide new insights into the optimum selection of metals for Schottky contacts on organic materials, with wider applications in light sensors and photovoltaic devices.

Organic field-effect transistors of poly(2,5-bis(3-dodecylthiophen-2-yl)thieno[2,3-b]thiophene) deposited on five different silane self-assembled monolayers.

Depositing a fused-ring thieno-thiophene polymer on different self-assembled monolayers indicates that varying the SAM surface energy changes the FET mobility and turn-on voltage by varying polymer crystallinity at the buried interface.

Designing solution-processable air-stable liquid crystalline crosslinkable semiconductors.

Organic electronics technology, in which at least the semiconducting component of the integrated circuit is an organic material, offers the potential for fabrication of electronic products by low-cost printing technologies, such as ink jet, gravure offset lithography and flexography. The products will typically be of lower performance than those using the present state of the art single crystal or polysilicon transistors, but comparable to amorphous silicon. A range of prototypes are under development, including rollable electrophoretic displays, active matrix liquid crystal (LC) displays, flexible organic light emitting diode displays, low frequency radio frequency identification tag and other low performance electronics. Organic semiconductors that offer both electrical performance and stability with respect to storage and operation under ambient conditions are required. This work describes the development of reactive mesogen semiconductors, which form large crosslinked LC domains on polymerization within mesophases. These crosslinked domains offer mechanical stability and are inert to solvent exposure in further processing steps. Reactive mesogens containing conjugated aromatic cores, designed to facilitate charge transport and provide good oxidative stability, were prepared and their liquid crystalline properties evaluated. The organization and alignment of the mesogens, both before and after crosslinking, were probed by grazing incidence wide-angle X-ray scattering of thin films. Both time-of-flight and field effect transistor devices were prepared and their electrical characterization reported.

Liquid-crystalline semiconducting polymers with high charge-carrier mobility.

Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths ( approximately 200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2-0.6 cm(2) V(-1) s(-1) achieved under nitrogen.