Explore the vast range of titles available.

A grand challenge in materials science is to identify the impact of molecular composition and structure across a range of length scales on macroscopic properties. We demonstrate a unified experimental–theoretical framework that coordinates experimental measurements of mesoscale structure with molecular-level physical modeling to bridge multiple scales of physical behavior. Here we apply this framework to understand charge transport in a semiconducting polymer. Spatially-resolved nanodiffraction in a transmission electron microscope is combined with a self-consistent framework of the polymer chain statistics to yield a detailed picture of the polymer microstructure ranging from the molecular to device relevant scale. Using these data as inputs for charge transport calculations, the combined multiscale approach highlights the underrepresented role of defects in existing transport models. Short-range transport is shown to be more chaotic than is often pictured, with the drift velocity accounting for a small portion of overall charge motion. Local transport is sensitive to the alignment and geometry of polymer chains. At longer length scales, large domains and gradual grain boundaries funnel charges preferentially to certain regions, creating inhomogeneous charge distributions. While alignment generally improves mobility, these funneling effects negatively impact mobility. The microstructure is modified in silico to explore possible design rules, showing chain stiffness and alignment to be beneficial while local homogeneity has no positive effect. This combined approach creates a flexible and extensible pipeline for analyzing multiscale functional properties and a general strategy for extending the accesible length scales of experimental and theoretical probes by harnessing their combined strengths.

Discotic (disk-shaped) molecules or molecular aggregates may form, within a certain temperature range, partially ordered phases, known as discotic liquid crystals, which have been extensively studied in the recent past. On the one hand, this interest was prompted by the fact that they represent models for testing energy and charge transport theories in organic materials. However, their long-range self-assembling properties, potential low cost, ease of processability with a variety of solvents and the relative ease of tailoring their properties via chemical synthesis, drove the attention of researchers also towards the exploitation of their semiconducting properties in organic electronic devices. This review covers recent research on the charge transport properties of discotic mesophases, starting with an introduction to their phase structure, followed by an overview of the models used to describe charge mobility in organic substances in general and in these systems in particular, and by the description of the techniques most commonly used to measure their charge mobility. The reader already familiar or not interested in such details can easily skip these sections and refer to the core section of this work, focusing on the most recent and significant results regarding charge mobility in discotic liquid crystals.

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior.

Thick active layers are crucial for scalable production of organic photodetectors (OPDs). However, most OPDs with active layers thicker than 200 nm typically exhibit decreased photocurrents and responsivities due to exciton diffusion and prolonged charge transport pathways. To address these limitations, we designed and synthesized PFBDT-8ttTPD, a fluorinated polymer donor. The strategic incorporation of fluorine effectively enhanced the charge carrier mobility, enabling more efficient charge transport, even in thicker films. OPDs combining PFBDT−8ttTPD with IT−4F or Y6 non-fullerene acceptors showed a substantially lower dark current density (Jd) for active layer thicknesses of 250−450 nm. Notably, Jd in the IT-4F-based devices declined from 8.74 × 10−9 to 4.08 × 10−10 A cm−2 under a reverse bias of −2 V, resulting in a maximum specific detectivity of 3.78 × 1013 Jones. Meanwhile, Y6 integration provided near-infrared sensitivity, with the devices achieving responsivity above 0.48 A W−1 at 850 nm and detectivity over 1013 Jones up to 900 nm, supporting broadband imaging. Importantly, high-quality thick films (≥400 nm) free of pinholes or defects were fabricated, enabling scalable production without performance loss. This advancement ensures robust photodetection in thick uniform layers and marks a significant step toward the development of industrially viable OPDs.

Donor–acceptor (D‐A) conjugated polymers have demonstrated great potential in organic field‐effect transistors application, and their aggregated structure is a crucial factor for high charge mobility. However, the aggregated structure of D‐A conjugated polymer films is complex and the structure–property relationship is difficult to understand. This review provides an overview of recent progress in controlling the aggregated structure of D‐A conjugated polymer films for higher mobility, including the mechanisms, methods, and properties. We first discuss the multilevel microstructures of D‐A conjugated polymer films, and then summarize the current understanding of the relationship between film microstructures and charge transport properties. Subsequently, we review the theory of D‐A conjugated polymer crystallization. After that, we summarize the common methods to control the aggregated structure of semi‐crystalline and near‐amorphous D‐A conjugated polymer films, such as crystallites and aggregates, tie chains, film alignment, and attempt to understand them from the basic theory of polymer crystallization. Finally, we provide the current challenges in controlling the aggregated structure of D‐A conjugated polymer films and in understanding the structure–property relationship. Donor‐acceptor (D‐A) conjugated polymers have demonstrated great potential in organic field‐effect transistors (OFETs) application, and their aggregated structure is a crucial factor for high charge mobility. This review provides an overview of recent progress in controlling the aggregated structure of semi‐crystalline and near‐amorphous D‐A conjugated polymers, including crystallization theories, control methods, aggregated structures, and charge mobilities.

Organic semiconductors are the focus of numerous studies; they are used in electronic devices. Modern research involves the production of neuromorphic organic materials, including those based on liquid crystal materials. The purpose of this work involves the theoretical modeling of molecules (the “core with branches” type) to construct a discotic mesophase capable of performing the functions of a neuromorphic material. For this purpose, the conductivity of crystal porphine, which can act as the nucleus of a molecule of the “core with branches” type, was investigated. The Marcus theory charge mobility values for the hole and electron were 0.148 and 0.088 cm2/V·s, respectively (the MOO method for calculating transfer integrals), and 0.561 and 0.160 cm2/V·s (DIPRO method). Based on TD-HF (HF-3c level of theory) calculations, possible structures of molecules for the formation of a discotic mesophase are proposed.

In this work, we investigate two recently synthesized naphthodithiophene diimide (NDTI) derivatives featuring promising n-type charge transport properties. We analyze the charge transport pathways and model charge mobility with the non-adiabatic hopping mechanism using the Marcus-Levich-Jortner rate constant formulation, highlighting the role of fluoroalkylated substitution in α (α-NDTI) and at the imide nitrogen (N-NDTI) position. In contrast with the experimental results, similar charge mobilities are computed for the two derivatives. However, while α-NDTI displays remarkably anisotropic mobilities with an almost one-dimensional directionality, N-NDTI sustains a more isotropic charge percolation pattern. We propose that the strong anisotropic charge transport character of α-NDTI is responsible for the modest measured charge mobility. In addition, when the role of thermally induced transfer integral fluctuations is investigated, the computed electron–phonon couplings for intermolecular sliding modes indicate that dynamic disorder effects are also more detrimental for the charge transport of α-NDTI than N-NDTI. The lower observed mobility of α-NDTI is therefore rationalized in terms of a prominent anisotropic character of the charge percolation pathways, with the additional contribution of dynamic disorder effects.

In this work, diamond/Si heterojunctions were fabricated by synthesizing a diamond layer directly on a monocrystalline n-type Si substrate. The diamond layers were characterized using micro-Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). The current–voltage (I–V) characteristics of the heterojunctions were measured at room temperature. The heterojunctions exhibited rectifying behavior, confirming their diode-like nature. Based on thermionic emission theory, key electrical parameters of the heterojunction diodes—including the ideality factor (n) and carrier mobility (μ)—were estimated from the I–V characteristics. The I–V curves revealed large ideality factors ranging from 1.5 to 6.5, indicating the presence of deep trap states with densities between 2 × 1015 and 8 × 1016 eV−1·cm−3. These variations were attributed to differences in the structural quality of the diamond layers and the effects of surface hydrogen termination.

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. We observe a universal scaling between the activation energy of the transistors and the interfacial thermal expansion mismatch, in which band-like transport is observed for similar CTEs, and activated transport otherwise. Our results provide evidence that a high-quality semiconductor layer is necessary, but not sufficient, to obtain efficient charge-carrier transport in devices, and underline the importance of holistic device design to achieve the intrinsic performance limits of a given organic semiconductor. We go on to show that insertion of an ultrathin CTE buffer layer mitigates this problem and can help achieve band-like transport on a wide range of substrate platforms.

2,9‐ and 2,10‐diphenylpentacene were synthesized by direct C−H borylation of ketal‐protected pentacene, followed by halodeboronation, resolution of the dihalo isomers, Suzuki arylation, cleavage of the ketals and decarbonylation in the solid state. They were studied as main active components in organic field effect transistors (OFETs). Diphenyl substitution of pentacene affects the unit cell dimensions only slightly, preserving a face to edge molecular packing in the first layers of thin films evaporated on SiO2 substrates. Both isomers self‐assemble into nanoribbons during the thin film growth upon vapor deposition. The similarity between the surface induced phases of the 2,9‐isomer and unsubstituted pentacene leads to similar 4‐probe hole mobilities, i. e. 0.13 cm2 V−1 s−1 for the former. Whereas 2,9‐disubstitution thus does essentially preserve the thin film characteristics of unsubstituted pentacene, 2,10‐disubstitution is detrimental to the molecular ordering in the thin films and therefore to the field effect mobility which is only 0.07 cm2 V−1 s−1. The known strong enhancement of field effect mobility observed upon diphenyl substitution of anthracene can thus not be emulated analogously with pentacene. Exploring morphological structures of new β‐Disubstituted pentacene derivatives: TEM optical micrographs and AFM topographies unveil the impact of chemical structure on 4‐probe field effect hole mobilities.