John G. Labram

Low band gap selenophene – diketopyrrolopyrrole polymers exhibiting high and balanced ambipolar performance in bottom-gate transistors

We report the synthesis of a selenophene–diketopyrrolopyrrole monomer and its co-polymerisation with selenophene and thieno[3,2-b]thiophene monomers by Stille coupling. The resulting low band gap polymers exhibit ambipolar charge transport in organic field effect transistors. High and balanced electron and hole mobilities in excess of 0.1 cm2 V−1 s−1 were observed in bottom-gate, bottom-contact devices, suggesting that selenophene inclusion is a promising strategy for the development of ambipolar organic semiconductors.

High Electron Mobility Thin-Film Transistors Based on Solution-Processed Semiconducting Metal Oxide Heterojunctions and Quasi-Superlattices

High mobility thin‐film transistor technologies that can be implemented using simple and inexpensive fabrication methods are in great demand because of their applicability in a wide range of emerging optoelectronics. Here, a novel concept of thin‐film transistors is reported that exploits the enhanced electron transport properties of low‐dimensional polycrystalline heterojunctions and quasi‐superlattices (QSLs) consisting of alternating layers of In2O3, Ga2O3, and ZnO grown by sequential spin casting of different precursors in air at low temperatures (180–200 °C). Optimized prototype QSL transistors exhibit band‐like transport with electron mobilities approximately a tenfold greater (25–45 cm2 V−1 s−1) than single oxide devices (typically 2–5 cm2 V−1 s−1). Based on temperature‐dependent electron transport and capacitance‐voltage measurements, it is argued that the enhanced performance arises from the presence of quasi 2D electron gas‐like systems formed at the carefully engineered oxide heterointerfaces. The QSL transistor concept proposed here can in principle extend to a range of other oxide material systems and deposition methods (sputtering, atomic layer deposition, spray pyrolysis, roll‐to‐roll, etc.) and can be seen as an extremely promising technology for application in next‐generation large area optoelectronics such as ultrahigh definition optical displays and large‐area microelectronics where high performance is a key requirement.

Temperature-Dependent Polarization in Field-Effect Transport and Photovoltaic Measurements of Methylammonium Lead Iodide

While recent improvements in the reported peak power conversion efficiency (PCE) of hybrid organic-inorganic perovskite solar cells have been truly astonishing, there are many fundamental questions about the electronic behavior of these materials. Here we have studied a set of electronic devices employing methylammonium lead iodide ((MA)PbI3) as the active material and conducted a series of temperature-dependent measurements. Field-effect transistor, capacitor, and photovoltaic cell measurements all reveal behavior consistent with substantial and strongly temperature-dependent polarization susceptibility in (MA)PbI3 at temporal and spatial scales that significantly impact functional behavior. The relative PCE of (MA)PbI3 photovoltaic cells is observed to reduce drastically with decreasing temperature, suggesting that such polarization effects could be a prerequisite for high-performance device operation.

Ambipolar organic transistors and near-infrared phototransistors based on a solution-processable squarilium dye†

Implementation of organic transistors in low-end, large-volume microelectronics depends, greatly, on the level of performance that can be achieved, but also on the compatibility of the technology with low-cost processing methodologies. Here we examine the suitability of a family of solution-processable zwitterionic molecules, so-called squarilium dyes, for the fabrication of organic ambipolar transistors and their application in (opto)electronic circuits. Ambipolar organic semiconductors and transistors are interesting because they could deliver performance characteristics (i.e. noise margins and signal gain) similar to that of complementary logic, but with the fabrication simplicity associated with unipolar logic (i.e. single semiconductor material and single type of metal electrodes). By designing squarilium dyes with appropriate electrochemical characteristics we demonstrate single-layer organic transistors that exhibit ambipolar charge transport with balanced electron and hole mobilities. By integrating a number of these ambipolar transistors we are also able to demonstrate complementary-like voltage inverters with wide noise margin and high signal gain. Another interesting feature of the squarilium dyes studied here is their strong absorption in the near-infrared (NIR) region of the electromagnetic spectrum. By exploring this interesting property we are able to demonstrate NIR light-sensing ambipolar organic transistors with promising operating characteristics.

Distinguishing the influence of structural and energetic disorder on electron transport in fullerene multi-adducts

Fullerene multi-adducts offer a method to tune the open-circuit voltage of organic solar cells but generally lead to poor photocurrent generation which has been linked to poor electron transport in the fullerenes. The poor electron transport may result from the effect of multiple side chains in hindering close packing of the fullerene cages or from disorder in energy levels due to the presence of multiple isomers. Here, we present time-of-flight and field-effect transistor measurements of mobility in [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) and its higher adducts. To understand the origin of the poor electron mobility, we develop a coarse-grained molecular dynamics model to build isomeric mixes of the multi-adducts. The coarse grained model massively speeds up the simulation relative to atomistic molecular dynamics, enabling assemblies of 100 000 molecules to be studied. We simulate electron transport in the structures using a kinetic Monte Carlo method, accounting for variations in site energy using electronic structure calculations. This allows us to separate the influence of packing disorder (poorer contact between fullerenes due to steric hindrance) from the influence of energetic disorder (due to varying acceptor energies of the isomers) on electron mobility. We find that energetic disorder due to different isomers dominates the trend in charge transport. Consequently, pure isomeric samples of higher fullerene adducts should enable higher efficiency solar cells.

Exploring Two-Dimensional Transport Phenomena in Metal Oxide Heterointerfaces for Next-Generation, High-Performance, Thin-Film Transistor Technologies.

In the last decade, metal oxides have emerged as a fascinating class of electronic material, exhibiting a wide range of unique and technologically relevant characteristics. For example, thin-film transistors formed from amorphous or polycrystalline metal oxide semiconductors offer the promise of low-cost, large-area, and flexible electronics, exhibiting performances comparable to or in excess of incumbent silicon-based technologies. Atomically flat interfaces between otherwise insulating or semiconducting complex oxides, are also found to be highly conducting, displaying 2-dimensional (2D) charge transport properties, strong correlations, and even superconductivity. Field-effect devices employing such carefully engineered interfaces are hoped to one day compete with traditional group IV or III-V semiconductors for use in the next-generation of high-performance electronics. In this Concept article we provide an overview of the different metal oxide transistor technologies and potential future research directions. In particular, we look at the recent reports of multilayer oxide thin-film transistors and the possibility of 2D electron transport in these disordered/polycrystalline systems and discuss the potential of the technology for applications in large-area electronics.

Main-Group Halide Semiconductors Derived from Perovskite: Distinguishing Chemical, Structural, and Electronic Aspects

Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.

Solution-processed dye-sensitized ZnO phototransistors with extremely high photoresponsivity

We report the fabrication of light-sensing thin-film transistors based on solution processed films of ZnO, as the channel material, functionalized with an organic dye as the light sensitizer. Due to the presence of the dye, the hybrid devices show exceptionally high photosensitivity to green light of 106 and a maximum photoresponsivity on the order of 104 A/W. The high performance is argued to be the result of the grain barrier limited nature of electron transport across the polycrystalline ZnO film and its dependence on charge carrier density upon illumination with green light. In addition to the excellent photoresponsivity and signal gain, the hybrid ZnO-dye photoactive layer exhibits high optical transparency. The unique combination of simple device fabrication and distinctive physical characteristics, such as optical transparency, renders the technology attractive for application in large-area transparent photodetectors.

Synthesis and characterisation of new diindenodithienothiophene (DITT) based materials

Three new diindenodithienothiophene (DITT) based materials were synthesised and their electrochemical properties investigated. The HOMO–LUMO gaps were observed to be 3.33, 3.48 and 2.81 eV, respectively. Cyclic voltammetry results indicate increased stability for the alkylated derivatives. The dioxide exhibits strong photoluminescence, giving a photoluminescence quantum yield of 0.72 in solution and 0.14 in the solid state. Hole mobility measurements were carried out on the non-alkylated derivative and the corresponding values were ∼10−4 cm2 V−1 s−1.

Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes

We report the preparation and X-ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene-iodine complex. The crystal structure contains infinite polyiodide I∞ (δ-) . Interestingly, the structure of iodine within the insoluble, blue starch-iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine. Close similarities in the low-wavenumber Raman spectra of the title compound and starch-iodine point to such infinite polyiodide chains in the latter as well.