Designing Contact Independent High-Performance Low-Cost Flexible Electronics.

Organic semiconductors enable low-cost solution processing of optoelectronic devices on flexible substrates. Their use in contemporary applications, however, is sparse due to persistent challenges in achieving the requisite performance levels in a reliable and reproducible manner. A critical bottleneck is the inefficiency associated with charge injection.

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers.

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT-TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H-C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties.

The Stark Effect: A Tool for the Design of High-Performance Molecular Rectifiers.

Molecular electronic devices offer a path to the miniaturization of electronic circuits and could potentially facilitate novel functionalities that can be embedded into the molecular structure. Given their nanoscale dimensions, device properties are strongly influenced by quantum effects, yet many of these phenomena have been largely overlooked. We investigated the mechanism responsible for current rectification in molecular diodes and found that efficient rectification is achieved by enhancing the Stark effect strength and enabling a large number of molecules to participate in transport.

Understanding radiation-generated electronic traps in radiation dosimeters based on organic field-effect transistors.

Organic dosimeters offer unique advantages over traditional technologies, and they can be used to expand the capabilities of current radiation detection systems. In-depth knowledge of the mechanisms underlying the interaction between radiation and organic materials is essential for their widespread adoption. Here, we identified and quantitatively characterized the electronic traps generated during the operation of radiation dosimeters based on organic field-effect transistors.

Introduction to nanomaterials for printed electronics.

An introduction to the themed collection on nanomaterials for printed electronics, featuring exciting research on a variety of nanomaterials and techniques used for printed electronics.

Humidity sensors based on molecular rectifiers.

Ambient humidity plays a key role in the health and well-being of us and our surroundings, making it necessary to carefully monitor and control it. To achieve this goal, several types of instruments based on various materials and operating principles have been developed. Reducing the production costs for such systems without affecting their sensitivity and reliability would allow for broader use and greater efficiency.

Intermolecular charge transfer enhances the performance of molecular rectifiers.

Molecular-scale diodes made from self-assembled monolayers (SAMs) could complement silicon-based technologies with smaller, cheaper, and more versatile devices. However, advancement of this emerging technology is limited by insufficient electronic performance exhibited by the molecular current rectifiers. We overcome this barrier by exploiting the charge-transfer state that results from co-assembling SAMs of molecules with strong electron donor and acceptor termini.

Dynamic self-stabilization in the electronic and nanomechanical properties of an organic polymer semiconductor.

The field of organic electronics has profited from the discovery of new conjugated semiconducting polymers that have molecular backbones which exhibit resilience to conformational fluctuations, accompanied by charge carrier mobilities that routinely cross the 1 cm/Vs benchmark. One such polymer is indacenodithiophene-co-benzothiadiazole. Previously understood to be lacking in microstructural order, we show here direct evidence of nanosized domains of high order in its thin films.

Organic single crystals of charge-transfer complexes: model systems for the study of donor/acceptor interactions.

The charge-transfer (CT) state arising as a hybrid electronic state at the interface between charge donor and charge acceptor molecular units is important to a wide variety of physical processes in organic semiconductor devices. The exact nature of this state depends heavily on the nature and co-facial overlap between the donor and acceptor; however, altering this overlap is usually accompanied by extensive confounding variations in properties due to extrinsic factors, such as microstructure. As a consequence, establishing reliable relationships between donor/acceptor molecular structures, their molecular overlap, degree of charge transfer and physical properties, is challenging.

Suppressing bias stress degradation in high performance solution processed organic transistors operating in air.

Solution processed organic field effect transistors can become ubiquitous in flexible optoelectronics. While progress in material and device design has been astonishing, low environmental and operational stabilities remain longstanding problems obstructing their immediate deployment in real world applications. Here, we introduce a strategy to identify the most probable and severe degradation pathways in organic transistors and then implement a method to eliminate the main sources of instabilities.

Photocurrent in Metal-Halide Perovskite/Organic Semiconductor Heterostructures: Impact of Microstructure on Charge Generation Efficiency.

Hybrid organic-inorganic metal-halide perovskites have emerged as versatile materials for enabling low-cost, mechanically flexible optoelectronic applications. The progress has been commendable; however, technological breakthroughs have outgrown the basic understanding of processes occurring in bulk and at device interfaces. Here, we investigated the photocurrent at perovskite/organic semiconductor interfaces in relation to the microstructure of electronically active layers.

Organic Field-Effect Transistors as Flexible, Tissue-Equivalent Radiation Dosimeters in Medical Applications.

Radiation therapy is one of the most prevalent procedures for cancer treatment, but the risks of malignancies induced by peripheral beam in healthy tissues surrounding the target is high. Therefore, being able to accurately measure the exposure dose is a critical aspect of patient care. Here a radiation detector based on an organic field-effect transistor (RAD-OFET) is introduced, an in vivo dosimeter that can be placed directly on a patient's skin to validate in real time the dose being delivered and ensure that for nearby regions an acceptable level of low dose is being received.

Structural Diversity in 2,2'-[Naphthalene-1,8:4,5-bis(dicarboximide)-'-diyl]-bis(ethylammonium) Iodoplumbates.

Crystallization from solutions containing 2,2'-[naphthalene-1,8:4,5-bis(dicarboximide)-'-diyl]-bis(ethylammonium) diiodide ((NDIC2)I) and PbI has been investigated. Eight different materials are obtained, either by variation of crystallization conditions or by subsequent thermal or solvent-induced transformations. Crystal structures have been determined for five materials.

Computationally aided design of a high-performance organic semiconductor: the development of a universal crystal engineering core.

Herein, we describe the design and synthesis of a suite of molecules based on a benzodithiophene "universal crystal engineering core". After computationally screening derivatives, a trialkylsilylethyne-based crystal engineering strategy was employed to tailor the crystal packing for use as the active material in an organic field-effect transistor. Electronic structure calculations were undertaken to reveal derivatives that exhibit exceptional potential for high-efficiency hole transport.

Molecular Rectifiers on Silicon: High Performance by Enhancing Top-Electrode/Molecule Coupling.

One of the simplest molecular-scale electronic devices is the molecular rectifier. In spite of considerable efforts aimed at understanding structure-property relationships in these systems, devices with predictable and stable electronic properties are yet to be developed. Here, we demonstrate highly efficient current rectification in a new class of compounds that form self-assembled monolayers on silicon.

A simple and robust approach to reducing contact resistance in organic transistors.

Efficient injection of charge carriers from the contacts into the semiconductor layer is crucial for achieving high-performance organic devices. The potential drop necessary to accomplish this process yields a resistance associated with the contacts, namely the contact resistance. A large contact resistance can limit the operation of devices and even lead to inaccuracies in the extraction of the device parameters.

The influence of isomer purity on trap states and performance of organic thin-film transistors.

Organic field-effect transistor (OFET) performance is dictated by its composition and geometry, as well as the quality of the organic semiconductor (OSC) film, which strongly depends on purity and microstructure. When present, impurities and defects give rise to trap states in the bandgap of the OSC, lowering device performance. Here, 2,8-difluoro-5,11-bis(triethylsilylethynyl)-anthradithiophene is used as a model system to study the mechanism responsible for performance degradation in OFETs due to isomer coexistence.

Crossover from band-like to thermally activated charge transport in organic transistors due to strain-induced traps.

The temperature dependence of the charge-carrier mobility provides essential insight into the charge transport mechanisms in organic semiconductors. Such knowledge imparts critical understanding of the electrical properties of these materials, leading to better design of high-performance materials for consumer applications. Here, we present experimental results that suggest that the inhomogeneous strain induced in organic semiconductor layers by the mismatch between the coefficients of thermal expansion (CTE) of the consecutive device layers of field-effect transistors generates trapping states that localize charge carriers.

Electron-phonon coupling in anthracene-pyromellitic dianhydride.

In this study, the electron-phonon coupling constants of the mixed-stack organic semiconductor anthracene-pyromellitic dianhydride (A-PMDA) are determined from experimental resonant Raman and absorption spectra of the charge transfer (CT) exciton using a time-dependent resonant Raman model. The reorganization energies of both intermolecular and intramolecular phonons are determined and compared with theoretical estimates derived from density functional theory calculations; they are found to agree well. We found that the dominant contribution to the total reorganization energy is due to intramolecular phonons, with intermolecular phonons only contributing a small percentage.

Solution-Processed Organic and Halide Perovskite Transistors on Hydrophobic Surfaces.

Solution-processable electronic devices are highly desirable due to their low cost and compatibility with flexible substrates. However, they are often challenging to fabricate due to the hydrophobic nature of the surfaces of the constituent layers. Here, we use a protein solution to modify the surface properties and to improve the wettability of the fluoropolymer dielectric Cytop.

Indacenodibenzothiophenes: synthesis, optoelectronic properties and materials applications of molecules with strong antiaromatic character.

Indeno[1,2-]fluorenes (IFs), while containing 4n π-electrons, are best described as two aromatic benzene rings fused to a weakly paratropic -indacene core. In this study, we find that replacement of the outer benzene rings of an IF with benzothiophenes allows the antiaromaticity of the central -indacene to strongly reassert itself. Herein we report a combined synthetic, computational, structural, and materials study of and indacenodibenzothiophenes (IDBTs).

Synthesis and Electrical Properties of Derivatives of 1,4-bis(trialkylsilylethynyl)benzo[2,3-b:5,6-b']diindolizines.

A new class of nitrogen-containing arene organic semiconductors incorporating fused indolizine units is described. This system, though having a zigzag shape, mimics the electronic properties of its linear analogue pentacene as a result of nitrogen lone pair incorporation into the π-electron system. Solubilizing trialkylsilylethynyl groups were employed to target crystal packing motifs appropriate for field-effect transistor devices.

Fluorinated benzalkylsilane molecular rectifiers.

We report on the synthesis and electrical properties of nine new alkylated silane self-assembled monolayers (SAMs) - (EtO)Si(CH)N = CHPhX where n = 3 or 11 and X = 4-CF 3,5-CF, 3-F-4-CF, 4-F, or 2,3,4,5,6-F, and explore their rectification behavior in relation to their molecular structure. The electrical properties of the films were examined in a metal/insulator/metal configuration, with a highly-doped silicon bottom contact and a eutectic gallium-indium liquid metal (EGaIn) top contact. The junctions exhibit high yields (>90%), a remarkable resistance to bias stress, and current rectification ratios (R) between 20 and 200 depending on the structure, degree of order, and internal dipole of each molecule.