Flexible Electronics Based on Organic Semiconductors: from Patterned Assembly to Integrated Applications

Organic flexible electronic devices are at the forefront of the electronics as they possess the potential to bring about a major lifestyle revolution owing to outstanding properties of organic semiconductors, including solution processability, lightweight and flexibility. For the integration of organic flexible electronics, the precise patterning and ordered assembly of organic semiconductors have attracted wide attention and gained rapid developments, which not only reduces the charge crosstalk between adjacent devices, but also enhances device uniformity and reproducibility. This review focuses on recent advances in the design, patterned assembly of organic semiconductors, and flexible electronic devices, especially for flexible organic field-effect transistors (FOFETs) and their multifunctional applications. First, typical organic semiconductor materials and material design methods are introduced. Based on these organic materials with not only superior mechanical properties but also high carrier mobility, patterned assembly strategies on flexible substrates, including one-step and two-step approaches are discussed. Advanced applications of flexible electronic devices based on organic semiconductor patterns are then highlighted. Finally, future challenges and possible directions in the field to motivate the development of the next generation of flexible electronics are proposed.     

Unconventional Nanofabrication for Supramolecular Electronics

The scientific effort toward achieving a full control over the correlation between structure and function in organic and polymer electronics has prompted the use of supramolecular interactions to drive the formation of highly ordered functional assemblies, which have been integrated into real devices. In the resulting field of supramolecular electronics, self‐assembly of organic semiconducting materials constitutes a powerful tool to generate low‐dimensional and crystalline functional architectures. These include 1D nanostructures (nanoribbons, nanotubes, and nanowires) and 2D molecular crystals with tuneable and unique optical, electronic, and mechanical properties. Optimizing the (opto)electronic properties of organic semiconducting materials is imperative to harness such supramolecular structures as active components for supramolecular electronics. However, their integration in real devices currently represents a significant challenge to the advancement of (opto)electronics. Here, an overview of the unconventional nanofabrication techniques and device configurations to enable supramolecular electronics to become a real technology is provided. A particular focus is put on how single and multiple supramolecular fibers and gels as well as supramolecularly engineered 2D materials can be integrated into novel vertical or horizontal junctions to realize flexible and high‐density multifunctional transistors, photodetectors, and memristors, exhibiting a set of new properties and excelling in their performances.     

Towards the Development of Flexible Non‐Volatile Memories

Flexible non‐volatile memories have attracted tremendous attentions for data storage for future electronics application. From device perspective, the advantages of flexible memory devices include thin, lightweight, printable, foldable and stretchable. The flash memories, resistive random access memories (RRAM) and ferroelectric random access memory/ferroelectric field‐effect transistor memories (FeRAM/FeFET) are considered as promising candidates for next generation non‐volatile memory device. Here, we review the general background knowledge on device structure, working principle, materials, challenges and recent progress with the emphasis on the flexibility of above three categories of non‐volatile memories.     

Fabric Organic Electrochemical Transistors for Biosensors

Flexible fabric biosensors can find promising applications in wearable electronics. However, high‐performance fabric biosensors have been rarely reported due to many special requirements in device fabrication. Here, the preparation of organic electrochemical transistors (OECTs) on Nylon fibers is reported. By introducing metal/conductive polymer multilayer electrodes on the fibers, the OECTs show very stable performance during bending tests. The devices with functionalized gates are successfully used as various biosensors with high sensitivity and selectivity. The fiber‐based OECTs are woven together with cotton yarns successfully by using a conventional weaving machine, resulting in flexible and stretchable fabric biosensors with high performance. The fabric sensors show much more stable signals in the analysis of moving aqueous solutions than planar devices due to a capillary effect in fabrics. The fabric devices are integrated in a diaper and remotely operated by using a mobile phone, offering a unique platform for convenient wearable healthcare monitoring.     

On the influence of silicon oxide nanoparticles on the optical and surface properties of hybrid (inorganic–organic) barrier materials

One of the major scientific and technological challenges for the production of flexible organic electronic devices is the device protection against atmospheric molecule permeation, which causes corrosion reducing its operation and lifetime. In this work, Spectroscopic Ellipsometry has been implemented to investigate the influence of silicon dioxide nanoparticles on the optical properties of hybrid polymers. The spectra analysis revealed valuable information about the electronic and vibrational response as well as the cross-linking mechanisms of these materials. The correlation of the optical properties with the synthesis parameters and the barrier response will contribute towards their optimization in order to be used as high barrier coatings for flexible organic electronics applications.     

Nonvolatile Memories Based on Graphene and Related 2D Materials

The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.     

Stretchable Organic Semiconductor Devices

Stretchable electronics are essential for the development of intensely packed collapsible and portable electronics, wearable electronics, epidermal and bioimplanted electronics, 3D surface compliable devices, bionics, prosthesis, and robotics. However, most stretchable devices are currently based on inorganic electronics, whose high cost of fabrication and limited processing area make it difficult to produce inexpensive, large‐area devices. Therefore, organic stretchable electronics are highly attractive due to many advantages over their inorganic counterparts, such as their light weight, flexibility, low cost and large‐area solution‐processing, the reproducible semiconductor resources, and the easy tuning of their properties via molecular tailoring. Among them, stretchable organic semiconductor devices have become a hot and fast‐growing research field, in which great advances have been made in recent years. These fantastic advances are summarized here, focusing on stretchable organic field‐effect transistors, light‐emitting devices, solar cells, and memory devices.     

A Robust Nonvolatile Resistive Memory Device Based on a Freestanding Ultrathin 2D Imine Polymer Film

Here, the synthesis of a wafer‐scale ultrathin 2D imine polymer (2DP) film with controllable thickness from simple benzene‐1,3,5‐tricarbaldehyde (BTA) and p‐phenylenediamine (PDA) building blocks is reported using a Schiff base polycondensation reaction at the air–water interface. The synthesized freestanding 2DP films are porous, insulating, and more importantly, covalently linked, which is ideally suited for nonvolatile memristors that use a conductive filament mechanism. These devices exhibit excellent switching performance with high reliability and reproducibility, with on/off ratios in the range of 10² to 10⁵ depending on the thickness of the film. In addition, the endurance and data retention capability of 2DP‐based nonvolatile resistive memristors are up to 200 cycles and 8 × 10⁴ s under constant voltage stress at 0.1 V. The intrinsic flexibility of the covalent organic polymer enables the fabrication of a flexible memory device on a polyimide film, which exhibits as reliable memory performance as that on the rigid substrate. Moreover, the 2DP‐based memory device shows outstanding thermal stability and organic solvent resistance, which are desirable properties for applications in wearable devices.     

Solution‐Processed Wide‐Bandgap Organic Semiconductor Nanostructures Arrays for Nonvolatile Organic Field‐Effect Transistor Memory

In this paper, the development of organic field‐effect transistor (OFET) memory device based on isolated and ordered nanostructures (NSs) arrays of wide‐bandgap (WBG) small‐molecule organic semiconductor material [2‐(9‐(4‐(octyloxy)phenyl)‐9H‐fluoren‐2‐yl)thiophene]3 (WG₃) is reported. The WG₃ NSs are prepared from phase separation by spin‐coating blend solutions of WG₃/trimethylolpropane (TMP), and then introduced as charge storage elements for nonvolatile OFET memory devices. Compared to the OFET memory device with smooth WG₃ film, the device based on WG₃ NSs arrays exhibits significant improvements in memory performance including larger memory window (≈45 V), faster switching speed (≈1 s), stable retention capability (>10⁴ s), and reliable switching properties. A quantitative study of the WG₃ NSs morphology reveals that enhanced memory performance is attributed to the improved charge trapping/charge‐exciton annihilation efficiency induced by increased contact area between the WG₃ NSs and pentacene layer. This versatile solution‐processing approach to preparing WG₃ NSs arrays as charge trapping sites allows for fabrication of high‐performance nonvolatile OFET memory devices, which could be applicable to a wide range of WBG organic semiconductor materials.     

25th Anniversary Article: Organic Electronics Marries Photochromism: Generation of Multifunctional Interfaces,Materials, and Devices

Organic semiconductors have garnered significant interest as key components for flexible, low‐cost, and large‐area electronics. Hitherto, both materials and processing thereof seems to head towards a mature technology which shall ultimately meet expectations and efforts built up over the past years. However, by its own organic electronics cannot compete or complement the silicon‐based electronics in integrating multiple functions in a small area unless novel solutions are brought into play. Photochromic molecules are small organic molecules able to undergo reversible photochemical isomerization between (at least) two (meta)stable states which exhibit markedly different properties. They can be embedded as additional component in organic‐based materials ready to be exploited in devices such as OLEDs, OFETs, and OLETs. The structurally controlled incorporation of photochromic molecules can be done at various interfaces of a device, including the electrode/semiconductor or dielectric/semiconductor interface, or even as a binary mixture in the active layer, in order to impart a light responsive nature to the device. This can be accomplished by modulating via a light stimulus fundamental physico‐chemical properties such as charge injection and transport in the device.     

A High‐Performance Optical Memory Array Based on Inhomogeneity of Organic Semiconductors

Organic optical memory devices keep attracting intensive interests for diverse optoelectronic applications including optical sensors and memories. Here, flexible nonvolatile optical memory devices are developed based on the bis[1]benzothieno[2,3‐d;2′,3′‐d′]naphtho[2,3‐b;6,7‐b′]dithiophene (BBTNDT) organic field‐effect transistors with charge trapping centers induced by the inhomogeneity (nanosprouts) of the organic thin film. The devices exhibit average mobility as high as 7.7 cm² V^?1 s^?1, photoresponsivity of 433 A W^?1, and long retention time for more than 6 h with a current ratio larger than 10⁶. Compared with the standard floating gate memory transistors, the BBTNDT devices can reduce the fabrication complexity, cost, and time. Based on the reasonable performance of the single device on a rigid substrate, the optical memory transistor is further scaled up to a 16 × 16 active matrix array on a flexible substrate with operating voltage less than 3 V, and it is used to map out 2D optical images. The findings reveal the potentials of utilizing [1]benzothieno[3,2‐b][1]benzothiophene (BTBT) derivatives as organic semiconductors for high‐performance optical memory transistors with a facile structure. A detailed study on the charge trapping mechanism in the derivatives of BTBT materials is also provided, which is closely related to the nanosprouts formed inside the organic active layer.     

High‐Performance Flexible Organic Nano‐Floating Gate Memory Devices Functionalized with Cobalt Ferrite Nanoparticles

Nano‐floating gate memory (NFGM) devices are transistor‐type memory devices that use nanostructured materials as charge trap sites. They have recently attracted a great deal of attention due to their excellent performance, capability for multilevel programming, and suitability as platforms for integrated circuits. Herein, novel NFGM devices have been fabricated using semiconducting cobalt ferrite (CoFe₂O₄) nanoparticles (NPs) as charge trap sites and pentacene as a p‐type semiconductor. Monodisperse CoFe₂O₄ NPs with different diameters have been synthesized by thermal decomposition and embedded in NFGM devices. The particle size effects on the memory performance have been investigated in terms of energy levels and particle–particle interactions. CoFe₂O₄ NP‐based memory devices exhibit a large memory window (≈73.84 V), a high read current on/off ratio (read I_on/I_off) of ≈2.98 × 10³_, and excellent data retention. Fast switching behaviors are observed due to the exceptional charge trapping/release capability of CoFe₂O₄ NPs surrounded by the oleate layer, which acts as an alternative tunneling dielectric layer and simplifies the device fabrication process. Furthermore, the NFGM devices show excellent thermal stability, and flexible memory devices fabricated on plastic substrates exhibit remarkable mechanical and electrical stability. This study demonstrates a viable means of fabricating highly flexible, high‐performance organic memory devices.     

Heterogeneous Monolithic Integration of Single‐Crystal Organic Materials

Manufacturing high‐performance organic electronic circuits requires the effective heterogeneous integration of different nanoscale organic materials with uniform morphology and high crystallinity in a desired arrangement. In particular, the development of high‐performance organic electronic and optoelectronic devices relies on high‐quality single crystals that show optimal intrinsic charge‐transport properties and electrical performance. Moreover, the heterogeneous integration of organic materials on a single substrate in a monolithic way is highly demanded for the production of fundamental organic electronic components as well as complex integrated circuits. Many of the various methods that have been designed to pattern multiple heterogeneous organic materials on a substrate and the heterogeneous integration of organic single crystals with their crystal growth are described here. Critical issues that have been encountered in the development of high‐performance organic integrated electronics are also addressed.     

Charge‐Storage Aromatic Amino Compounds for Nonvolatile Organic Transistor Memory Devices

Here, charge‐storage nonvolatile organic field‐effect transistor (OFET) memory devices based on interfacial self‐assembled molecules are proposed. The functional molecules contain various aromatic amino moieties (N‐phenyl‐N‐pyridyl amino‐ (PyPN), N‐phenyl amino‐ (PN), and N,N‐diphenyl amino‐ (DPN)) which are linked by a propyl chain to a triethoxysilyl anchor group and act as the interface modifiers and the charge‐storage elements. The PyPN‐containing pentacene‐based memory device (denoted as PyPN device) presents the memory window of 48.43 V, while PN and DPN devices show the memory windows of 24.88 and 8.34 V, respectively. The memory characteristic of the PyPN device can remain stable along with 150 continuous write‐read‐erase‐read cycles. The morphology analysis confirms that three interfacial layers show aggregation due to the N atomic self‐catalysis and hydrogen bonding effects. The large aggregate‐covered PyPN layer has the full contact area with the pentacene molecules, leading to the high memory performance. In addition, the energy level matching between PyPN molecules and pentacene creates the smallest tunneling barrier and facilitates the injection of the hole carriers from pentacene to the PyPN layer. The experimental memory characteristics are well in agreement with the computational calculation.     

Controlling Molecular Doping in Organic Semiconductors

The field of organic electronics thrives on the hope of enabling low‐cost, solution‐processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution‐processed p‐type doped polymeric semiconductors. Highlighted topics include how solution‐processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication—applications beyond those directly analogous to inorganic doping.     

Electrostatic Properties of Ideal and Non‐ideal Polar Organic Monolayers: Implications for Electronic Devices

Molecules in (or as) electronic devices are attractive because the variety and flexibility inherent in organic chemistry can be harnessed towards a systematic design of electrical properties. Specifically, monolayers of polar molecules introduce a net dipole, which controls surface and interface barriers and enables chemical sensing via dipole modification. Due to the long range of electrostatic phenomena, polar monolayer properties are determined not only by the type of molecules and/or bonding configuration to the substrate, but also by size, (dis‐)order, and adsorption patterns within the monolayer. Thus, a comprehensive understanding of polar monolayer characteristics and their influence on electronic devices requires an approach that transcends typical chemical designs, i.e., one that incorporates long‐range effects, in addition to short‐range effects due to local chemistry. We review and explain the main uses of polar organic monolayers in shaping electronic device properties, with an emphasis on long‐range cooperative effects and on the differences between electrical properties of uniform and non‐uniform monolayers.     

Organic Photodetectors for Next-Generation Wearable Electronics

Next-generation wearable electronics will need to be mechanically flexible and stretchable such that they can be conformally attached onto the human body. Photodetectors that are available in today's market are based on rigid inorganic crystalline materials and they have limited mechanical flexibility. In contrast, photodetectors based on organic polymers and molecules have emerged as promising alternatives due to their inherent mechanical softness, ease of processing, tunable optoelectronic properties, good light sensing performance, and biocompatibility. Here, the recent advances of organic photodetectors in terms of both optoelectronic and mechanical properties are outlined and discussed, and their application in wearable electronics including health monitoring sensors, artificial vision, and self-powering integrated devices are highlighted.     

Organic Ferroelectric‐Based 1T1T Random Access Memory Cell Employing a Common Dielectric Layer Overcoming the Half‐Selection Problem

Organic electronics based on poly(vinylidenefluoride/trifluoroethylene) (P(VDF‐TrFE)) dielectric is facing great challenges in flexible circuits. As one indispensable part of integrated circuits, there is an urgent demand for low‐cost and easy‐fabrication nonvolatile memory devices. A breakthrough is made on a novel ferroelectric random access memory cell (1T1T FeRAM cell) consisting of one selection transistor and one ferroelectric memory transistor in order to overcome the half‐selection problem. Unlike complicated manufacturing using multiple dielectrics, this system simplifies 1T1T FeRAM cell fabrication using one common dielectric. To achieve this goal, a strategy for semiconductor/insulator (S/I) interface modulation is put forward and applied to nonhysteretic selection transistors with high performances for driving or addressing purposes. As a result, high hole mobility of 3.81 cm² V^?1 s^?1 (average) for 2,6‐diphenylanthracene (DPA) and electron mobility of 0.124 cm² V^?1 s^?1 (average) for N ,N ′‐1H,1H‐perfluorobutyl dicyanoperylenecarboxydiimide (PDI‐FCN₂) are obtained in selection transistors. In this work, we demonstrate this technology's potential for organic ferroelectric‐based pixelated memory module fabrication.     

Long‐Lived Flexible Displays Employing Efficient and Stable Inverted Organic Light‐Emitting Diodes

Although organic light‐emitting diodes (OLEDs) are promising for use in applications such as in flexible displays, reports of long‐lived flexible OLED‐based devices are limited due to the poor environmental stability of OLEDs. Flexible substrates such as plastic allow ambient oxygen and moisture to permeate into devices, which degrades the alkali metals used for the electron‐injection layer in conventional OLEDs (cOLEDs). Here, the fabrication of a long‐lived flexible display is reported using efficient and stable inverted OLEDs (iOLEDs), in which electrons can be effectively injected without the use of alkali metals. The flexible display employing iOLEDs can emit light for over 1 year with simplified encapsulation, whereas a flexible display employing cOLEDs exhibits almost no luminescence after only 21 d with the same encapsulation. These results demonstrate the great potential of iOLEDs to replace cOLEDs employing alkali metals for use in a wide variety of flexible organic optoelectronic devices.     

Flexible/Stretchable Supercapacitors with Novel Functionality for Wearable Electronics

With the miniaturization of personal wearable electronics, considerable effort has been expended to develop high-performance flexible/stretchable energy storage devices for powering integrated active devices. Supercapacitors can fulfill this role owing to their simple structures, high power density, and cyclic stability. Moreover, a high electrochemical performance can be achieved with flexible/stretchable supercapacitors, whose applications can be expanded through the introduction of additional novel functionalities. Here, recent advances in and future prospects for flexible/stretchable supercapacitors with innate functionalities are covered, including biodegradability, self-healing, shape memory, energy harvesting, and electrochromic and temperature tolerance, which can contribute to reducing e-waste, ensuring device integrity and performance, enabling device self-charging following exposure to surrounding stimuli, displaying the charge status, and maintaining the performance under a wide range of temperatures. Finally, the challenges and perspectives of high-performance all-in-one wearable systems with integrated functional supercapacitors for future practical application are discussed.