Self‐Assembled Hybrid Materials Based on Organic Nanocrystals and Carbon Nanotubes

Organic crystalline materials are used as dyes/pigments, pharmaceuticals, and active components of photonic and electronic devices. There is great interest in integrating organic crystals with inorganic and carbon nanomaterials to create nanocomposites with enhanced properties. Such efforts are hampered by the difficulties in interfacing organic crystals with dissimilar materials. Here, an approach that employs organic nanocrystallization is presented to fabricate solution‐processed organic nanocrystal/carbon nanotube (ONC/CNT) hybrid materials based on readily available organic dyes (perylene diimides (PDIs)) and carbon nanotubes. The hybrids are prepared by self‐assembly in aqueous media to afford free‐standing films with tunable CNT content. These exhibit excellent conductivities (as high as 5.78 ± 0.56 S m^?1), and high thermal stability that are superior to common polymer/CNT hybrids. The color of the hybrids can be tuned by adding various PDI derivatives. ONC/CNT hybrids represent a novel class of nanocomposites, applicable as optoelectronic and conductive colorant materials.     

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.     

Advanced Carbon for Flexible and Wearable Electronics

Flexible and wearable electronics are attracting wide attention due to their potential applications in wearable human health monitoring and care systems. Carbon materials have combined superiorities such as good electrical conductivity, intrinsic and structural flexibility, light weight, high chemical and thermal stability, ease of chemical functionalization, as well as potential mass production, enabling them to be promising candidate materials for flexible and wearable electronics. Consequently, great efforts are devoted to the controlled fabrication of carbon materials with rationally designed structures for applications in next‐generation electronics. Herein, the latest advances in the rational design and controlled fabrication of carbon materials toward applications in flexible and wearable electronics are reviewed. Various carbon materials (carbon nanotubes, graphene, natural‐biomaterial‐derived carbon, etc.) with controlled micro/nanostructures and designed macroscopic morphologies for high‐performance flexible electronics are introduced. The fabrication strategies, working mechanism, performance, and applications of carbon‐based flexible devices are reviewed and discussed, including strain/pressure sensors, temperature/humidity sensors, electrochemical sensors, flexible conductive electrodes/wires, and flexible power devices. Furthermore, the integration of multiple devices toward multifunctional wearable systems is briefly reviewed. Finally, the existing challenges and future opportunities in this field are summarized.     

Self‐Assembled α‐Cyanostilbenes for Advanced Functional Materials

In the specific context of condensed media, the significant and increasing recent interest in the α‐cyanostilbene (CS) motif [? Ar? CH?C(CN)? Ar? ] is relevant. These compounds have shown remarkable optical features in addition to interesting electrical properties, and hence they are recognized as very suitable and versatile options for the development of functional materials. This progress report is focused on current and future use of CS structures and molecular assemblies with the aim of exploring and developing for the next generations of functional materials. A critical selection of illustrative materials that contain the CS motif, including relevant subfamilies such as the dicyanodistyrylbenzene and 2,3,3‐triphenylacrylonitrile shows how, driven by the self‐assembly of CS blocks, a variety of properties, effects, and possibilities for practical applications can be offered to the scientific community, through different rational routes for the elaboration of advanced materials. A survey is provided on the research efforts directed toward promoting the self‐assembly of the solid state (polycrystalline solids, thin films, and single crystals), liquid crystals, nanostructures, and gels with multistimuli responsiveness, and applications for sensors, organic light‐emitting diodes, organic field effect transistors, organic lasers, solar cells, or bioimaging purposes.     

Printable Transparent Conductive Films for Flexible Electronics

Printed electronics are an important enabling technology for the development of low‐cost, large‐area, and flexible optoelectronic devices. Transparent conductive films (TCFs) made from solution‐processable transparent conductive materials, such as metal nanoparticles/nanowires, carbon nanotubes, graphene, and conductive polymers, can simultaneously exhibit high mechanical flexibility, low cost, and better photoelectric properties compared to the commonly used sputtered indium‐tin‐oxide‐based TCFs, and are thus receiving great attention. This Review summarizes recent advances of large‐area flexible TCFs enabled by several roll‐to‐roll‐compatible printed techniques including inkjet printing, screen printing, offset printing, and gravure printing using the emerging transparent conductive materials. The preparation of TCFs including ink formulation, substrate treatment, patterning, and postprocessing, and their potential applications in solar cells, organic light‐emitting diodes, and touch panels are discussed in detail. The rational combination of a variety of printed techniques with emerging transparent conductive materials is believed to extend the opportunities for the development of printed electronics within the realm of flexible electronics and beyond.     

Photopatterning of Cross‐Linkable Epoxide‐Functionalized Block Copolymers and Dual‐Tone Nanostructure Development for Fabrication Across the Nano‐ and Microscales

The self‐assembly of block copolymers in thin films provides an attractive approach to patterning 5–100 nm structures. Cross‐linking and photopatterning of the self‐assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar‐forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self‐assembly and cross‐linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross‐linkable block copolymer materials in thin films and enable simultaneous structure formation across scales—micrometer scale patterns achieved by photolithography and nanostructures via self‐assembly of the block copolymer. Such materials and processes are thus shown to be capable of self‐assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.     

2D Organic Materials for Optoelectronic Applications

The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D‐materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self‐assembly monolayers, and covalent organic frameworks. The protocols for 2D‐organic‐crystal‐fabrication and ‐patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.     

A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template‐Assisted Assembly of Polyfluorene Nanowires

DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self‐assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self‐assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar‐like arrays and well‐positioned concentric ring‐like superstructures composed of DNAs are formed. Subsequently, the ring‐like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9‐bis(6′‐N,N,N‐trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA‐templated PF2 nanowires to yield two DNA/PF2‐based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors.     

Stretchable,Large‐area Organic Electronics

Stretchability will significantly expand the application scope of electronics, particularly large‐area electronics—displays, sensors, and actuators. If arbitrary surfaces and movable parts could be covered with stretchable electronics, which is impossible with conventional electronics, new classes of applications are expected to emerge. A large hurdle is manufacturing electrical wiring with high conductivity, high stretchability, and large‐area compatibility. This Review describes stretchable, large‐area electronics based on organic field‐effect transistors for applications to sensors and displays. First, novel net‐shaped organic transistors are employed to realize stretchable, large‐area sensor networks that detect distributions of pressure and temperature simultaneously. The whole system is functional even when it is stretched by 25%. In order to further improve stretchability, printable elastic conductors are developed by dispersing single‐walled carbon nanotubes (SWNTs) as dopants uniformly in rubbers. Further, we describe integration of printable elastic conductors with organic transistors to construct a rubber‐like stretchable active matrix for large‐area sensor and display applications. Finally, we will discuss the future prospects of stretchable, large‐area electronics with delineating a picture of the next‐generation human/machine interfaces from the aspect of materials science and electronic engineering.     

Perovskite Materials for Light‐Emitting Diodes and Lasers

Organic–inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light‐emitting diodes, lasers, and light‐emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light‐emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A^?1 have been achieved. Although perovskite light‐emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light‐emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower‐dimensionality layered and three‐dimensional perovskites, nanostructures, charge‐transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light‐emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light‐emitting devices.     

Investigation of the optical properties of polyfluorene/ZnO nanocomposites

Polyfluorene (PF) and its derivatives are very promising candidates for organic light emitting diodes (OLEDs) in lighting applications because of their high photoluminescence and electroluminescence efficiencies. Recent investigations of potential materials for OLEDs have shown that introducing n-type inorganic nanoparticles into conjugated polymers is efficient to produce stable and high performance devices. In this study, composite thin films made by incorporation of zinc oxide (ZnO) nanoparticles into a PF derivative have been prepared and their optical properties have been investigated.The prepared thin films were stored in different media (in air, in vacuum, in the dark or exposed to light) in order to study environmental influences on the material stability. Analysis of spectral data obtained from infrared (IR), Raman, UV-vis, and photoluminescence (PL) measurements shows a large enhancement in luminescence for polymer nanocomposites while using high nanoparticle concentrations (within a limit of 10% ZnO). Time-resolved PL performed on those nanocomposite films corroborated the above result: it indicated that the light-emission enhancement can be explained by efficient energy transfer from nanoparticles to the polymer chains and increase of the chain separation distance. In addition, the nanocomposites were found to be more stable than pristine polymer films whatever the storage conditions were used. It was confirmed by IR analysis that incorporation of nanoparticles into polymers prohibited the formation of fluorenonyl groups in PF chains, which was identified as the main cause of the degradation of the polymer under photo-oxidation.     

Beta‐Sheet‐Forming,Self‐Assembled Peptide Nanomaterials towards Optical,Energy, and Healthcare Applications

Peptide self‐assembly is an attractive route for the synthesis of intricate organic nanostructures that possess remarkable structural variety and biocompatibility. Recent studies on peptide‐based, self‐assembled materials have expanded beyond the construction of high‐order architectures; they are now reporting new functional materials that have application in the emerging fields such as artificial photosynthesis and rechargeable batteries. Nevertheless, there have been few reviews particularly concentrating on such versatile, emerging applications. Herein, recent advances in the synthesis of self‐assembled peptide nanomaterials (e.g., cross β‐sheet‐based amyloid nanostructures, peptide amphiphiles) are selectively reviewed and their new applications in diverse, interdisciplinary fields are described, ranging from optics and energy storage/conversion to healthcare. The applications of peptide‐based self‐assembled materials in unconventional fields are also highlighted, such as photoluminescent peptide nanostructures, artificial photosynthetic peptide nanomaterials, and lithium‐ion battery components. The relation of such functional materials to the rapidly progressing biomedical applications of peptide self‐assembly, which include biosensors/chips and regenerative medicine, are discussed. The combination of strategies shown in these applications would further promote the discovery of novel, functional, small materials.     

Carbon Nanotube‐Quantum Dot Nanohybrids: Coupling with Single‐Particle Control in Aqueous Solution

A strategy is reported for the controlled assembly of organic‐inorganic heterostructures consisting of individual single‐walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT‐QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD‐based optoelectronic and light‐energy conversion devices.     

Organic Light‐Emitting Transistors: Materials,Device Configurations,and Operations

Organic light‐emitting transistors (OLETs) represent an emerging class of organic optoelectronic devices, wherein the electrical switching capability of organic field‐effect transistors (OFETs) and the light‐generation capability of organic light‐emitting diodes (OLEDs) are inherently incorporated in a single device. In contrast to conventional OFETs and OLEDs, the planar device geometry and the versatile multifunctional nature of OLETs not only endow them with numerous technological opportunities in the frontier fields of highly integrated organic electronics, but also render them ideal scientific scaffolds to address the fundamental physical events of organic semiconductors and devices. This review article summarizes the recent advancements on OLETs in light of materials, device configurations, operation conditions, etc. Diverse state‐of‐the‐art protocols, including bulk heterojunction, layered heterojunction and laterally arranged heterojunction structures, as well as asymmetric source‐drain electrodes, and innovative dielectric layers, which have been developed for the construction of qualified OLETs and for shedding new and deep light on the working principles of OLETs, are highlighted by addressing representative paradigms. This review intends to provide readers with a deeper understanding of the design of future OLETs.     

Thermal and aqueous stability improvement of graphene oxide enhanced diphenylalanine nanocomposites

Abstract

Nanocomposites of diphenylalanine (FF) and carbon based materials provide an opportunity to overcome drawbacks associated with using FF micro- and nanostructures in nanobiotechnology applications, in particular their poor structural stability in liquid solutions. In this study, FF/graphene oxide (GO) composites were found to self-assemble into layered micro- and nanostructures, which exhibited improved thermal and aqueous stability. Dependent on the FF/GO ratio, the solubility of these structures was reduced to 35.65% after 30 min as compared to 92.4% for pure FF samples. Such functional nanocomposites may extend the use of FF structures to e.g. biosensing, electrochemical, electromechanical or electronic applications.     

Coordination‐Driven Hierarchical Assembly of Hybrid Nanostructures Based on 2D Materials

2D materials have received tremendous scientific and engineering interests due to their remarkable properties and broad‐ranging applications such as energy storage and conversion, catalysis, biomedicine, electronics, and so forth. To further enhance their performance and endow them with new functions, 2D materials are proposed to hybridize with other nanostructured building blocks, resulting in hybrid nanostructures with various morphologies and structures. The properties and functions of these hybrid nanostructures depend strongly on the interfacial interactions between 2D materials and other building blocks. Covalent and coordination bonds are two strong interactions that hold high potential in constructing these robust hybrid nanostructures based on 2D materials. However, most 2D materials are chemically inert, posing problems for the covalent assembly with other building blocks. There are usually coordination atoms in most of 2D materials and their derivatives, thus coordination interaction as a strong interfacial interaction has attracted much attention. In this review, recent progress on the coordination‐driven hierarchical assembly based on 2D materials is summarized, focusing on the synthesis approaches, various architectures, and structure–property relationship. Furthermore, insights into the present challenges and future research directions are also presented.     

Hierarchical 3D All‐Carbon Composite Structure Modified with N‐Doped Graphene Quantum Dots for High‐Performance Flexible Supercapacitors

Flexible supercapacitors have shown enormous potential for portable electronic devices. Herein, hierarchical 3D all‐carbon electrode materials are prepared by assembling N‐doped graphene quantum dots (N‐GQDs) on carbonized MOF materials (cZIF‐8) interweaved with carbon nanotubes (CNTs) for flexible all‐solid‐state supercapacitors. In this ternary electrode, cZIF‐8 provides a large accessible surface area, CNTs act as the electrical conductive network, and N‐GQDs serve as highly pseudocapactive materials. Due to the synergistic effect and hierarchical assembly of these components, N‐GQD@cZIF‐8/CNT electrodes exhibit a high specific capacitance of 540 F g^?1 at 0.5 A g^?1 in a 1 m H₂SO₄ electrolyte and excellent cycle stability with 90.9% capacity retention over 8000 cycles. The assembled supercapacitor possesses an energy density of 18.75 Wh kg^?1 with a power density of 108.7 W kg^?1. Meanwhile, three supercapacitors connected in series can power light‐emitting diodes for 20 min. All‐solid‐state N‐GQD@cZIF‐8/CNT flexible supercapacitor exhibits an energy density of 14 Wh kg^?1 with a power density of 89.3 W kg^?1, while the capacitance retention after 5000 cycles reaches 82%. This work provides an effective way to construct novel electrode materials with high energy storage density as well as good cycling performance and power density for high‐performance energy storage devices via the rational design.     

Layer‐by‐Layer Hydrogen‐Bonded Polymer Films: From Fundamentals to Applications

Recent years have seen increasing interest in the construction of nanoscopically layered materials involving aqueous‐based sequential assembly of polymers on solid substrates. In the booming research area of layer‐by‐layer (LbL) assembly of oppositely charged polymers, self‐assembly driven by hydrogen bond formation emerges as a powerful technique. Hydrogen‐bonded (HB) LbL materials open new opportunities for LbL films, which are more difficult to produce than their electrostatically assembled counterparts. Specifically, the new properties associated with HB assembly include: 1) the ease of producing films responsive to environmental pH at mild pH values, 2) numerous possibilities for converting HB films into single‐ or two‐component ultrathin hydrogel materials, and 3) the inclusion of polymers with low glass transition temperatures (e.g., poly(ethylene oxide)) within ultrathin films. These properties can lead to new applications for HB LbL films, such as pH‐ and/or temperature‐responsive drug delivery systems, materials with tunable mechanical properties, release films dissolvable under physiological conditions, and proton‐exchange membranes for fuel cells. In this report, we discuss the recent developments in the synthesis of LbL materials based on HB assembly, the study of their structure–property relationships, and the prospective applications of HB LbL constructs in biotechnology and biomedicine.     

Multifunctional Nanocomposites with High Strength and Capacitance Using 2D MXene and 1D Nanocellulose

The family of two‐dimensional (2D) metal carbides and nitrides, known as MXenes, are among the most promising electrode materials for supercapacitors thanks to their high metal‐like electrical conductivity and surface‐functional‐group‐enabled pseudocapacitance. A major drawback of these materials is, however, the low mechanical strength, which prevents their applications in lightweight, flexible electronics. A strategy of assembling freestanding and mechanically robust MXene (Ti₃C₂T_x ) nanocomposites with one‐dimensional (1D) cellulose nanofibrils (CNFs) from their stable colloidal dispersions is reported. The high aspect ratio of CNF (width of ≈3.5 nm and length reaching tens of micrometers) and their special interactions with MXene enable nanocomposites with high mechanical strength without sacrificing electrochemical performance. CNF loading up to 20%, for example, shows a remarkably high mechanical strength of 341 MPa (an order of magnitude higher than pristine MXene films of 29 MPa) while still maintaining a high capacitance of 298 F g^?1 and a high conductivity of 295 S cm^?1. It is also demonstrated that MXene/CNF hybrid dispersions can be used as inks to print flexible micro‐supercapacitors with precise dimensions. This work paves the way for fabrication of robust multifunctional MXene nanocomposites for printed and lightweight structural devices.     

Development of new transparent conductors and device applications utilizing a multidisciplinary approach

Transparent and conductive films are key components for optoelectronic devices. They are applied as n-type transparent electrical contacts for inorganic and organic light emitting diodes, solar cells and flat panel displays as well as p- and n-type active semiconductive oxides to setup wide band gap p-n junctions and devices for the emerging field of transparent and radiation hard electronics.The demand for these films is strongly increasing due to the extensive market growth in these areas but the solutions available today only partially fulfill the requirements on low resistivity, high transmittance, large area deposition, low cost manufacturing, and ability for fine patterning, light scattering and precise alignment of the electronic structure to surrounding semiconductors.The cooperation of five Fraunhofer Institutes within the “Fraunhofer Project MAVO METCO” aims towards establishing fundamental knowledge and control about the defect chemistry, structure and morphology of the transparent semiconductive oxides. The goal is to achieve materials with outstanding properties such as n-type transparent conductive oxides with tailored work function and excellent durability, novel delafossite based p-type materials allowing cost effective large area deposition, oxide based p-n heterojunctions and Ag based electrodes to be used for thin film photovoltaics and organic light emitting diodes.Starting from first-principle modelling of the electronic structure, we address the development of new transparent conductive layers by PVD and Sol-Gel ending up with device implementation for OLEDs and organic as well as Si based a-Si:H/µc-Si:H and HIT solar cells.