Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

http://absimage.aps.org/image/MAR14/MWS_MAR14-2013-020288.pdf

A general relationship between disorder, aggregation and charge transport in conjugated polymers

In this review, we describe the developments in the field of naphthalene diimides (NDIs) from 2016 to the presentday. NDIs are shown to be an increasingly interesting class of molecules due to their electronic properties, large electron deficient aromatic cores and tendency to self-assemble into functional structures. Almost all NDIs possess high electron affinity, good charge carrier mobility, and excellent thermal and oxidative stability, making them promising candidates for applications in organic electronics, photovoltaic devices, and flexible displays. NDIs have also been extensively studied due to their potential real-world uses across a wide variety of applications including supramolecular chemistry, sensing, host–guest complexes for molecular switching devices, such as catenanes and rotaxanes, ion-channels, catalysis, and medicine and as non-fullerene accepters in solar cells. In recent years, NDI research with respect to supramolecular assemblies and mechanoluminescent properties has also gained considerable traction. Thus, this review will assist a wide range of readers and researchers including chemists, physicists, biologists, medicinal chemists and materials scientists in understanding the scope for development and applicability of NDI dyes in their respective fields through a discussion of the main properties of NDI derivatives and of the status of emerging applications.

Naphthalene diimides: perspectives and promise.

Recent decades have witnessed the rapid development of semiconducting polymers in terms of high charge mobilities and applications in transistors. Significant efforts have been made to develop various conjugated frameworks and linkers. However, studies are increasingly demonstrating that the side chains of semiconducting polymers can significantly affect interchain packing, thin film crystallinity, and thus semiconducting performance. Ways to modify the side alkyl chains to improve the interchain packing order and charge mobilities for conjugated polymers are first discussed. It is shown that modifying the branching chains by moving the branching points away from the backbones can boost the charge mobilities, which can also be improved through partially replacing branching chains with linear ones. Second, the effects of side chains with heteroatoms and functional groups are discussed. The siloxane-terminated side chains are utilized to enhance the semiconducting properties. The fluorinated alkyl chains are beneficial for improving both charge mobility and air stability. Incorporating H bonding group side chains can improve thin film crystallinities and boost charge mobilities. Notably, incorporating functional groups (e.g., glycol, tetrathiafulvalene, and thymine) into side chains can improve the selectivity of field-effect transistor (FET)-based sensors, while photochromic group containing side chains in conjugated polymers result in photoresponsive semiconductors and optically tunable FETs.

https://onlinelibrary.wiley.com/doi/epdf/10.1002/adma.201903104

The Effects of Side Chains on the Charge Mobilities and Functionalities of Semiconducting Conjugated Polymers beyond Solubilities.

https://pubs.rsc.org/en/content/articlepdf/2019/PY/C9PY00793H

Photoresponsive polymers with multi-azobenzene groups

Recent research interest in organic field‐effect transistor (FET) memory has shifted to the functionality of photoprogramming in terms of its potential uses in multibit data storage and light‐assisted encryption and its low‐energy consumption and broad response to various optical bands. Phototransistor memory can be modulated through both electrical stress and light illumination, allowing it to function as an orthogonal operation method without mutual interference. Herein, the basic design concepts, requirements, and architectures of phototransistor memory are introduced. Design architectures such as channel‐only, channel‐with‐photogate, photochromatic channel devices and floating gate, photoactive polymer, and organic molecule‐based electrets are systematically categorized. The operational mechanism and impact of effective combinations of channels and electrets are reviewed to provide a fundamental understanding of photoprogramming as well as its potential future developmental applications as nonvolatile memory. Furthermore, recent advances in phototransistors and their diverse applications, including nonvolatile memory, artificial synapses, and photodetectors, are summarized. Finally, the outlook for the future development of phototransistors is briefly discussed. A comprehensive picture of the recent progress in phototransistors is provided.

Recent Advances in Organic Phototransistors: Nonvolatile Memory, Artificial Synapses, and Photodetectors

Semiconducting conjugated polymers with photoswitching behavior are highly demanded for field‐effect transistors (FETs) with tunable electronic properties. Herein a new design strategy is established for photoresponsive conjugated polymers by incorporating photochromic units (azobenzene) into the flexible side alkyl chains. It is shown that azobenzene groups in the side chains of the DPP (diketopyrrolopyrrole)‐quaterthiophene polymer (PDAZO) can undergo trans/cis photoisomerization in fully reversible and fast manner. Optically tunable FETs with bistable states are successfully fabricated with thin films of PDAZO. The drain‐source currents are reduced by 80.1% after UV light irradiation for ≈28 s, which are easily restored after further visible light irradiation for ≈33 s. Such fast optically tunable FETs are not reported before. Moreover, such current photomodulation can be implemented for multiple light irradiation cycles with good photofatigue resistance. Additionally, thin film charge mobility of PDAZO can be reversibly modulated by alternating UV and visible light irradiations. On the basis of theoretical calculations and GIWAXS data, it is hypothesized that the dipole moment and configuration changes associated with the trans‐/cis‐photoisomerization of azobenzene groups in PDAZO can affect the respective intra‐chain and inter‐chain charge transporting, which is responsible for the optically tunable behavior for FETs with thin films of PDAZO.

Optically Tunable Field Effect Transistors with Conjugated Polymer Entailing Azobenzene Groups in the Side Chains

n-Type organic/polymeric semiconductors with high electron mobilities are highly demanded for future flexible organic circuits. Except for developing a new conjugated backbone, recent studies show that side-chain engineering also plays an indispensable role in boosting the charge-transporting property. In this paper, we report a new polymer PNDI2T-DTD with a representative n-type naphthalene diimide (NDI)-bithiophene backbone for high-performance n-type flexible thin-film transistors through branching/linear side-chain engineering strategy. Serving as the flexible side chains, the linear/branching side-chain pattern is found to be effective in tuning the preaggregation behavior in solution and the packing ordering of polymeric chains, resulting in the improvement of thin-film crystallinity. The electron mobility of the thin film of PNDI2T-DTD on flexible substrates can reach 1.52 cm2 V-1 s-1, which is approximately five times higher than that of PNDI2T-DT with the same conjugated backbone and only branching alkyl chains.

Improving the Electronic Transporting Property for Flexible Field-Effect Transistors with Naphthalene Diimide-Based Conjugated Polymer through Branching/Linear Side-Chain Engineering Strategy

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Optically Tunable Field Effect Transistors with Conjugated Polymer Entailing Azobenzene Groups in the Side Chains

Improving the Electronic Transporting Property for Flexible Field-Effect Transistors with Naphthalene Diimide-Based Conjugated Polymer through Branching/Linear Side-Chain Engineering Strategy