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Gastrointestinal (GI) mucus is a biologically complex hydrogel that acts as a partially permeable barrier between the contents of the GI tract and the mucosal epithelial lining. Its structural integrity is essential for the lubrication of the tract thereby aiding smooth transit of contents, and the protection of the epithelium from pathogens that seek to colonise and invade. Understanding its physical response to drugs and the microbiome is essential for treating many gastrointestinal infectious diseases. Given this, a static in vitro model of a GI mucus-on-a-chip has been developed with integrated electronics to monitor the barrier properties of mucus hydrogels. Its application for investigating the effect of drugs and biofilm formation on the mucus structure is validated using rheological techniques, confocal microscopy and electrochemical impedance spectroscopy (EIS). [ABSTRACT FROM AUTHOR]

Organic electrochemical transistors (OECTs) have shown great potential in bioelectronics to transduce small biological signals for applications such as the electrical recording of excitable cells and assessing cell barrier properties. It is imperative that operating the OECT as a biosensor does not affect the biological system. However, bias voltages applied to channel materials such as the conducting polymer (CP) PEDOT:PSS have been shown to induce the formation of hydrogen peroxide (H2O2) which can disrupt the physiology of cells. In this work, we evaluated the impact of H2O2 formation during OECT operation by comparing an oxygen-sensitive CP (PEDOT:PSS) and an oxygen-stable CP (p(gPyDPP-MeOT2)). While both CPs show high biocompatibility in their non-biased, resting state, we observed large differences during the operation of the electrochemical device. OECTs with PEDOT:PSS produce H2O2 where the H2O2 concentration in the electrolyte depends on the channel area and the time of operation. In comparison, OECTs using the oxygen-stable DPP-based polymer showed no sign of H2O2 formation. Further investigation also revealed how the proliferation rate of neuronal cells directly interfaced with such OECTs was affected by the concentration of H2O2. Our work demonstrated the limitations of oxygen-sensitive OECT channel materials for bioelectronic applications and provides guidance for material design strategies to develop safe bioelectronic devices for real-life applications. [ABSTRACT FROM AUTHOR]

Self-doping organic semiconductors provide a promising route to avoid instabilities and morphological issues associated with molecular n-type dopants. Structural characterization of a naphthalenetetracarboxylic diimide (NDI) semiconductor covalently bound to an ammonium hydroxide group is presented. The dopant precursor was found to be the product of an unexpected base catalyzed hydrolysis, which was reversible. The reversible hydrolysis had profound consequences on the chemical composition, morphology, and electronic performance of the doped films. In addition, we investigated the degradation mechanism of the quaternary ammonium group and the subsequent doping of NDI. These findings reveal that the products of more than one chemical reaction during processing of films must be considered when utilizing this promising class of water-soluble semiconductors. [ABSTRACT FROM AUTHOR]

Supported lipid bilayers (SLBs) are cell–membrane-mimicking platforms of varying biological complexity, that can be formed on solid surfaces and used to characterise the properties of the plasma membrane or to study membrane interactions at the molecular level. The incorporation of microfabricated electrodes and transistors has allowed for their electrochemical characterisation using techniques such as Electrochemical Impedance Spectroscopy (EIS) and transistor-based impedance spectroscopy. In this work, we combine experimental data with numerical simulation to explore the relationship between changes in SLB quality and impedance output, delving into a deeper understanding of the impedance profiles of devices with and without SLB, as well as extracted parameters such as membrane resistance (Rm). We extrapolate this approach to investigate the relationship between microelectrode area and sensor sensitivity to changes in SLB state, towards rational device design. We highlight the trend of electrode size (polymer volume) required for sensing bilayer presence as well as the dependence of the electrode sensitivity to the SLB capacitance and resistance. Finally, we illustrate how our flexible approach of including electrode and transistor measurements to amalgamate characteristic impedance spectra of transistors, overcomes the problem of low frequency noise and errors seen with traditional EIS. [ABSTRACT FROM AUTHOR]

Conjugated polymers are widely used as photoactive and transport layers in organic and hybrid photovoltaics (PV), where the energetics of polymers are a key design criterion. Here, we show that significant variations in terminal molecular ordering between top and bottom surfaces of a wide range of conjugated polymer films can result in sizable interfacial ionization energy (IE) differences by as much as 0.33 eV, which has significant impact on organic and hybrid PV devices. Such tunability is surprisingly seen even in nominally amorphous polymers. We devise a strategy leveraging wet and dry laminations to form donor–acceptor planar heterojunction (PHJ) devices using exposed and buried surfaces of donor polymers and demonstrate meaningful influence over the open circuit voltage (VOC) by up to 0.32 V. We use this insight to devise a controlled intermixing approach which yields superior VOC and JSC to conventional bulk heterojunction devices by leveraging the disordered interface to maximize VOC and the greater aggregation of the donor to increase the JSC. We go on to demonstrate how judicious control of polymer surface IE benefits charge extraction in colloidal quantum dot PV devices in the role of hole transport layers. Our results show that polymer interfacial and bulk properties are both critical to the functionality of optoelectronic devices and should both be given prime consideration when designing heterojunction devices. [ABSTRACT FROM AUTHOR]

We have recently developed a strategy to improve charge percolation efficiency in a renowned family of naphthalene-diimide bithiophene (PNDI-T2) copolymers, based on the application of a tailored thermal treatment on pre-aligned films. Here we show that the accurate choice of thermal post-processing temperatures can induce a notable lamellar thickening and an improvement of molecular alignment, the latter being favored by alkyl chains with longer branches. Correspondingly, enhanced transport properties are observed. Interestingly, these are found to be independent of lamellar thickness. In fact, within this family of molecules, characterized by a locked non-planar conformation and strong intramolecular charge localization, the orientational order within charge percolation paths was found to be the only factor dictating charge transport. [ABSTRACT FROM AUTHOR]

The ability to control the charge density of organic mixed ionic electronic conductors (OMIECs) via reactions with redox-active analytes has enabled applications as electrochemical redox sensors. Their charge density-dependent conductivity can additionally be tuned via charge injection from electrodes, for instance in organic electrochemical transistors (OECTs), where volumetric charging of the OMIEC channel enables excellent transconductance and amplification of low potentials. Recent efforts have combined the chemical detection with the transistor function of OECTs to achieve compact electrochemical sensors. However, these sensors often fall short of the expected amplification performance of OECTs. Here, we investigate the operation mechanism of various OECT architectures to deduce the design principles required to achieve reliable chemical detection and signal amplification. By utilizing a non-polarizable gate electrode and conducting the chemical reaction in a compartment separate from the OECT, the recently developed Reaction Cell OECT achieves reliable modulation of the OECT channel's charge density. This work demonstrates that systematic and rational design of OECT chemical sensors requires understanding the electrochemical processes that result in changes in the potential (charge density) of the channel, the underlying phenomenon behind amplification. [ABSTRACT FROM AUTHOR]

We employ X-ray diffraction, NMR and UV-vis spectroscopy techniques to shed light on the structure, molecular mobility and crystallization of a prototypical semiconducting polymer poly(3-(2′-ethylhexyl)thiophene) (P3EHT). Grazing-incidence X-ray diffraction (GIXD) and high-field 1H–1H double-quantum NMR reveal a tilt of the thiophene rings along the main chains, while high resolution 13C solid-state NMR methods show the presence of highly mobile side-chains. Taken together, the data reveal a high amount of free volume between adjacent chains in the crystalline phase, most likely owing to the additional steric hindrance from the branched ethyl group of the hexyl side chains. Additionally, the aforementioned methods allow us to confirm that crystallization in P3EHT occurs in a one-dimensional fashion along the polymer backbone. An extended model based on the Avrami principles is used to fit the experimental results to extract key parameters, such as nucleation rate and density, that govern these crystallization processes. The results show significantly reduced rates of crystallization in thin P3EHT thin films due to polymer chain confinement effects. [ABSTRACT FROM AUTHOR]

Solar cells based on semiconductor materials with low diffusion lengths like organics and amorphous silicon exhibit short circuit currents and energy conversion efficiencies distinctly below the detailed balance limit (commonly called the Shockley Queisser limit). The short circuit current and energy conversion efficiency of such solar cells can be increased by employing a 3D device architecture. The 3D device architecture leads to a distinct gain in the optical thickness of such solar cells compared to a conventional planar solar cell, while the electrical thickness of the investigated 3D and planar solar cells is equal. Hence a short circuit current can be achieved close to the theoretical upper limit. In this study, a 3D organic solar cell is studied. The influence of the 3D architecture on the solar cell performance parameters of a small molecule organic solar cell was investigated. Finite-difference time-domain optical simulations are utilized to determine the quantum efficiency and short circuit current of the 3D solar cell structure. A guideline is provided on how to achieve a high energy conversion efficiency with a 3D solar cell. The proposed approach is not only applicable to organic solar cells. The approach is applicable to all solar energy materials with low diffusion length and/or low charge carrier mobility. [ABSTRACT FROM AUTHOR]

Semiconducting polymers based on diketopyrrolopyrrole have achieved high charge carrier mobilities in field-effect transistors due to their strong intermolecular interactions, which lead to a high structural order that is beneficial for charge transport. One factor that influences the degree of order in thin films is the choice of solubilizing side chains. In this study, we present a new polymer, poly{3-([2,2′:5′,2′′-terthiophen]-5-yl)-2,5-bis(6-dodecyloctadecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione-6,5′′-diyl}, which has extended side chains and side-chain branching points that were moved further away from the polymer backbone. Bottom-gate, top-contact field-effect transistors from solution sheared films of this material show average saturation hole mobilities of close to 1 cm2 V−1 s−1 which is higher than in devices of a commonly used version of this polymer with shorter side chains. The increase in mobility is attributed to an improved structural order in the thin-film state and a decrease in π–π stacking distance. The fabricated devices show very good air-stability without significant degradation in performance after more than one year storage under ambient conditions. [ABSTRACT FROM AUTHOR]

Many organic electronic devices require vertically layered structures to operate. This manuscript demonstrates an additive solution process for depositing multiple layers of semiconducting polymer (SP) films by controlling film solubility with molecular dopants. During multi-layer deposition the bottom layers are exposed to a series of solvent environments that swell the SP films. We use neutron reflectometry (NR) to quantify the film thickness change and solvent content during solvent exposure in a single poly-3-hexylthiophene (P3HT) layer. The film thickness increases by 40–80% with exposure to good solvents. Four layer thin-films composed of alternating protonated and deuterated P3HT layers were additively coated from solution. NR measurements reveal high individual layer purity and that extensive solvent soaking induces no mixing between layers. Finally, two-point conductivity measurements demonstrate that P3HT:P3HT layer interfaces have no effect on vertical conductivity. This facile process enables additive layering of mutually soluble SP films and can be used to design novel electronic device architectures. [ABSTRACT FROM AUTHOR]

Here we show that the blending of structurally similar oligothiophene molecules is an effective approach to improve the field-effect mobility and Ion/Ioff as compared to single component based transistors. The effect of addition of each component is studied extensively using a wide array of methods such as X-ray diffraction, ToF-SIMS, and ambient UPS correlated with the electrical characterization. [ABSTRACT FROM AUTHOR]

In conjugated polymers and small molecules of organic solar cells, aggregation induced by intermolecular interactions governs the performance of photovoltaics. However, little attention has been paid to the connection between molecular structure and aggregation within solar cells based on soluble small molecules. Here we demonstrate modulation of intermolecular aggregation of two synthesized molecules through heteroatom substitution to develop an understanding of the role of aggregation in conjugated molecules. Molecule 1 (M1) based on 2-ethylhexyloxy-benzene substituted benzo[1,2-b:4,5-b′]dithiophene (BDTP) and diketopyrrolopyrrole (DPP) displays strong aggregation in commonly used organic solvents, which is reduced in molecule 2 (M2) by facile oxygen atom substitution on the BDTP unit confirmed by absorption spectroscopy and optical microscopy, while it successfully maintains molecular planarity and favorable charge transport characteristics. Solar cells based on M2 exhibit more than double the photocurrent of devices based on M1 and yield a power conversion efficiency of 5.5%. A systematic investigation of molecular conformation, optoelectronic properties, molecular packing and crystallinity as well as film morphology reveals structure dependent aggregation responsible for the performance difference between the two conjugated molecules. [ABSTRACT FROM AUTHOR]

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure and phase morphology. Hence, it is of central importance to manipulate―from the outset―the molecular arrangement and packing of this special class of polymers from the nano- to the micrometer scale when they are integrated in thin film devices such as photovoltaic cells, transistors or light-emitting diodes, for example. One effective strategy for this purpose is to vary their molecular weight. The reason for this is that materials of different weight-average molecular weight (Mw) lead to different microstructures. Polymers of low Mw form unconnected, extended-chain crystals because of their non-entangled nature. As a result, a polycrystalline, one-phase morphology is obtained. In contrast, high-Mw materials, in which average chain lengths are longer than the length between entanglements, form two-phase morphologies comprised of crystalline moieties embedded in largely un-ordered (amorphous) regions. Here, we discuss how changes in these structural features affect exciton dissociation processes. We utilise neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw as a model system and apply time-resolved photoluminescence (PL) spectroscopy to probe the electronic landscape in a range of P3HT thin-film architectures. We find that at 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Tellingly, both the amplitude and decay-rate distribution depend strongly on Mw. In films with dominant one-phase, chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges. Its decay is significantly slower than in two-phase microstructures. We therefore conclude that excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure, in agreement with previous work [Paquin et al., Phys. Rev. Lett., 2011, 106, 197401]. We note, however, that independent of Mw, the delayed-PL lineshape due to charge recombination is representative of that in low-Mw microstructures. We thus hypothesize that charge recombination at these low temperatures―and likely also charge generation―occur in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, producing a delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. [ABSTRACT FROM AUTHOR]

Zinc oxide (ZnO) is a wide-band gap II–VI semiconductor with various optoelectronic applications owing to its transparency to visible light and tunable optical/electronic properties achieved by doping. While exquisite morphology control has been demonstrated for colloidal cadmium-chalcogenide II–VI nanocrystals over the past two decades, shape control strategies for solution-grown anisotropic ZnO nanocrystals (＜100 nm) are limited in scope – they suffer from large polydispersities and highly branched nanorods. Here, we present a modular synthetic design approach that overcomes many of the synthetic challenges associated with zinc oxide nanorods and enables nearly independent control of morphology and impurity incorporation. Manipulation of alcoholysis reaction kinetics through multiple precursor solution injections and judicious use of phosphonic acid surfactants enables the synthesis of nanorods with highly tunable shapes, lengths (40–200 nm), diameters (6–80 nm), and doping levels (with aluminum – Al3+– cations). This work will enable further studies on shape-dependent phenomena in colloidal metal oxide nanorods as well as facilitate understanding of doping and plasmonics in anisotropic nanoscale metal oxide systems. [ABSTRACT FROM AUTHOR]

Conductive fullerene (C60) units were designed to be arranged in one dimensional close contact by locally organizing them with covalent bonds in a spatially constrained manner. Combined molecular dynamics and quantum chemical calculations predicted that the intramolecular electronic interactions (i.e. charge transport) between the pendant C60 units could be controlled by the length of the spacers linking the C60 units and the polymer main chain. In this context, C60 side-chain polymers with high relative degrees of polymerization up to 1220 and fullerene compositions up to 53% were synthesized by ruthenium catalyzed ring-opening metathesis polymerization of the corresponding norbornene-functionalized monomers. UV/vis absorption and photothermal deflection spectra corroborated the enhanced inter-fullerene interactions along the polymer chains. The electron mobility measured for the thin film field-effect transistor devices from the polymers was more than an order of magnitude higher than that from the monomers, as a result of the stronger electronic coupling between the adjacent fullerene units within the long polymer chains. This molecular design strategy represents a general approach to the enhancement of charge transport properties of organic materials via covalent bond-based organization. [ABSTRACT FROM AUTHOR]

Conducting polymers (CPs) are increasingly being used to interface with cells for applications in both bioelectronics and tissue engineering. To facilitate this interaction, cells need to adhere and grow on the CP surface. Extracellular matrix components are usually necessary to support or enhance cell attachment and growth on polymer substrates. Here we show the preparation of PEDOT(TOS):gelatin composites as a new biocompatible substrate for use in tissue engineering. Gelatin, a derivative of the extracellular matrix protein collagen, was incorporated into poly(3,4 ethylenedioxythiophene)-tosylate (PEDOT(TOS)) films via vapour phase polymerisation (VPP) without changing the electrochemical properties of the CP. Further, gelatin, incorporated into the PEDOT(TOS) film, was found to specifically support bovine brain capillary endothelial cell adhesion and growth, indicating that the functionality of the biomolecule was maintained. The biocompatibility of the composite films was demonstrated indicating the significant future potential of biocomposites of this type for use in promoting cell adhesion in electrically active materials for tissue engineering. [ABSTRACT FROM AUTHOR]

The promise of lead halide hybrid perovskites for optoelectronic applications makes finding less-toxic alternatives a priority. The double perovskite Cs 2 AgBiBr 6 ( 1 ) represents one such alternative, offering long carrier lifetimes and greater stability under ambient conditions. However, the large and indirect 1.95 eV bandgap hinders its potential as a solar absorber. Here we report that alloying crystals of 1 with up to 1 atom% Sn results in a bandgap reduction of up to ca. 0.5 eV while maintaining low toxicity. Crystals can be alloyed with up to 1 atom% Sn and the predominant substitution pathway appears to be a ∼2 : 1 substitution of Sn 2+ and Sn 4+ for Ag + and Bi 3+ , respectively, with Ag + vacancies providing charge compensation. Spincoated films of 1 accommodate a higher Sn loading, up to 4 atom% Sn, where we see mostly Sn 2+ substitution for both Ag + and Bi 3+ . Density functional theory (DFT) calculations ascribe the bandgap redshift to the introduction of Sn impurity bands below the conduction band minimum of the host lattice. Using optical absorption spectroscopy, photothermal deflection spectroscopy, X-ray absorption spectroscopy, 119 Sn NMR, redox titration, single-crystal and powder X-ray diffraction, multiple elemental analysis and imaging techniques, and DFT calculations, we provide a detailed analysis of the Sn content and oxidation state, dominant substitution sites, and charge-compensating defects in Sn-alloyed Cs 2 AgBiBr 6 ( 1:Sn ) crystals and films. An understanding of heterovalent alloying in halide double perovskites opens the door to a wider breadth of potential alloying agents for manipulating their band structures in a predictable manner., (This journal is © The Royal Society of Chemistry 2019.)