The solvent effect on the morphology and molecular ordering of benzothiadiazole-based small molecule for inkjet-printed thin-film transistors.

A small molecule organic semiconductor, D(D'-A-D')2 comprising benzothiadiazole as an acceptor, 3-hexylthiophene, and thiophene as donors, was successfully synthesized. X-ray diffraction and atomic force microscopy were used to investigate the effect of a dual solvent system with varying ratios of chloroform and toluene on film crystallinity and film morphology via inkjet printing. The film prepared with a chloroform to toluene ratio of 1.5 : 1 showed better performance with improved crystallinity and morphology due to having enough time to control the arrangement of molecules. In addition, by optimizing ratios of CHCl3 to toluene, the inkjet-printed TFT based on 3HTBTT using a CHCl3 and toluene ratio of 1.5 : 1 was successfully fabricated and exhibited a hole mobility of 0.01 cm2 V-1 s-1 due to the improved molecular ordering of the 3HTBTT film.

Truly form-factor-free industrially scalable system integration for electronic textile architectures with multifunctional fiber devices.

An integrated textile electronic system is reported here, enabling a truly free form factor system via textile manufacturing integration of fiber-based electronic components. Intelligent and smart systems require freedom of form factor, unrestricted design, and unlimited scale. Initial attempts to develop conductive fibers and textile electronics failed to achieve reliable integration and performance required for industrial-scale manufacturing of technical textiles by standard weaving technologies. Here, we present a textile electronic system with functional one-dimensional devices, including fiber photodetectors (as an input device), fiber supercapacitors (as an energy storage device), fiber field-effect transistors (as an electronic driving device), and fiber quantum dot light-emitting diodes (as an output device). As a proof of concept applicable to smart homes, a textile electronic system composed of multiple functional fiber components is demonstrated, enabling luminance modulation and letter indication depending on sunlight intensity.

Smart textile lighting/display system with multifunctional fibre devices for large scale smart home and IoT applications.

Smart textiles consist of discrete devices fabricated from-or incorporated onto-fibres. Despite the tremendous progress in smart textiles for lighting/display applications, a large scale approach for a smart display system with integrated multifunctional devices in traditional textile platforms has yet to be demonstrated. Here we report the realisation of a fully operational 46-inch smart textile lighting/display system consisting of RGB fibrous LEDs coupled with multifunctional fibre devices that are capable of wireless power transmission, touch sensing, photodetection, environmental/biosignal monitoring, and energy storage. The smart textile display system exhibits full freedom of form factors, including flexibility, bendability, and rollability as a vivid RGB lighting/grey-level-controlled full colour display apparatus with embedded fibre devices that are configured to provide external stimuli detection. Our systematic design and integration strategies are transformational and provide the foundation for realising highly functional smart lighting/display textiles over large area for revolutionary applications on smart homes and internet of things (IoT).

Sequential structural degradation of red perovskite quantum dots and its prevention by introducing iodide at a stable gradient concentration into the core-shell red perovskite quantum dots.

Perovskite quantum dots (QDs) have been extensively studied as emissive materials for next-generation optoelectronics due to their outstanding optical properties; however, their structural instabilities, specifically those of red perovskite QDs, are critical obstacles in realizing operationally reliable perovskite QD-based optoelectronic devices. Accordingly, herein, we investigated the sequential degradation mechanism of red perovskite QDs upon their exposure to an electric field. Via electrical and chemical characterization, we demonstrated that degradation occurred in the following order: anion-defect-assisted halide migration, cation-defect-assisted migration of I-/Cs+ ions, defective gradient I ion distribution, structural distortion, and ion transport/I2 vaporization with defect proliferation. Among these steps, the defective gradient I ion distribution is the key process in the structural degradation of perovskite QDs. Based on our findings, we designed perovskite/SiO2 core-shell QDs with stable gradient I concentrations. Most notably, the operational stabilities of perovskite QD-light-emitting diodes (PeLEDs) fabricated using the perovskite/SiO2 core-shell QDs were approximately 5000 times those of the PeLEDs constructed using pristine perovskite QDs.

Synthesis of Chemically Stable Ultrathin SiO2-Coated Core-Shell Perovskite QDs via Modulation of Ligand Binding Energy for All-Solution-Processed Light-Emitting Diodes.

Recently, perovskite quantum dots (QDs) have attracted intensive interest due to their outstanding optical properties, but their extremely poor chemical stability hinders the development of the high-performance perovskite QD-based light-emitting diodes (PeLEDs). In this study, chemically stable SiO2-coated core-shell perovskite QDs are prepared to fabricate all-solution-processed PeLEDs. When the SiO2 shell thickness increases, the chemical stability of perovskite QDs is dramatically improved, while the charge injection efficiency is significantly decreased, which becomes the biggest obstacle for PeLED applications. Thus, controlling the SiO2 thickness is essential to obtain core-shell perovskite QDs optimal for PeLEDs in an aspect of chemical and optoelectrical properties. The 3-aminopropyl-triethoxysilane (APTES)/oleylamine (OAm) volume ratio is found to be a critical factor for obtaining an ultrathin SiO2 shell. Optimization of the APTES/OAm ratio affords A-site-doped CsPbBr3 QDs with an ultrathin SiO2 shell (A-CsPbBr3@SiO2 QDs) that exhibit longer radiative lifetimes and smaller shallow trap fraction than those without A-site doping, resulting in a higher photoluminescence quantum yield. A-CsPbBr3@SiO2 QDs also demonstrate long-term superior chemical stability in polar solvents without loss of optical properties due to passivation by the SiO2 shell and less defects via A-site doping. Consequently, all-solution-processed PeLED is successfully fabricated under ambient conditions, facilitating perovskite QD utilization in low-cost, large-area, flexible next-generation displays.

Design of Chemically Stable Organic Perovskite Quantum Dots for Micropatterned Light-Emitting Diodes through Kinetic Control of a Cross-Linkable Ligand System.

Perovskite quantum dot (QD) light-emitting diodes (PeLEDs) are ideal for next-generation display applications because of their excellent color purity, high efficiency, and cost-effective fabrication. However, developing a technology for high-resolution multicolor patterning of perovskite QDs remains challenging, owing to the chemical instability of these materials. To overcome these issues, in this work, the generation of surface defects is prevented by controlling the ligand-binding kinetics using a stable ligand system (Stable LS). The crystalline reconstruction of perovskite QDs after addition of the Stable LS results in an ≈18% increase in their photoluminescence quantum yield in solution and it also improves the ambient stability of the perovskite QD solution. Moreover, the perovskite QDs with Stable LS can undergo cross-linking under UV irradiation. The tightly bridged perovskite QDs effectively prevent moisture-assisted ligand dissociation in film state due to the increased hydrophobicity and restricted movement of the cross-linked surface ligands. Thus, the cross-linked perovskite QD film shows improved chemical/environmental stability without substantial deterioration in optoelectrical properties. As a result, a white electroluminescent device with high resolution (≈1 µm) is successfully fabricated by inkjet printing using green and red perovskite QDs.

Energy/Charge Transfer Modulation with Spacer Ligands for Highly Emissive Quantum Dot-Polymer Blend.

A blend of perovskite quantum dots (QDs) and a hole transport layer (HTL) is a feasible candidate to solve the long-standing issues in light-emitting diodes (LEDs) such as charge injection, energy state matching, and defect passivation. However, QD:HTL blend structures for QD-based LEDs suffer from fast charge and energy transfers due to an inhomogeneous distribution of QDs and the HTL matrix. Here we report new cross-linkable spacer ligands between QDs and TFB that result in a highly emissive QD:TFB-blended LED device. We synthesize three representative spacer ligands to control the charge and energy transfers between QDs and the HTL. The first spacer ligand is used for controlling the molecular distance between QDs and TFB, and the second spacer ligand is designed to investigate how molecular interaction between QDs and the spacer ligand affects the optical property of the QD:TFB blend. Subsequently, the best spacer ligand, a 10-((2-benzoylbenzoyl)oxy)decanoic acid, is designed to anchor TFB (via a benzophenone group) and simultaneously bond to QDs (with a carboxylic acid functional group). The carboxylic acid group strongly interacts with QDs, dramatically improving the cross-linking rate between QDs and TFB. Due to the direct interaction between QDs and TFB, hole carriers can be effectively injected to perovskite QDs through the conductive backbone of TFB, resulting in the highest luminance values of 10917 cd/m2 at 7.4 V due to carrier injection balance. This is at least 10 times better LED performance compared with a pristine QD device.

Modeling Electrical Percolation to optimize the Electromechanical Properties of CNT/Polymer Composites in Highly Stretchable Fiber Strain Sensors.

A simulation model of electrical percolation through a three-dimensional network of curved CNTs is developed in order to analyze the electromechanical properties of a highly stretchable fiber strain sensor made of a CNT/polymer composite. Rigid-body movement of the curved CNTs within the polymer matrix is described analytically. Random arrangements of CNTs within the composite are generated by a Monte-Carlo simulation method and a union-find algorithm is utilized to investigate the network percolation. Consequently, the strain-induced resistance change curves are obtained in a wide strain range of the composite. In order to compare our model with experimental results, two CNT/polymer composite fibers were fabricated and tested as strain sensors. Their effective CNT volume fractions are estimated by comparing the experimental data with our simulation model. The results confirm that the proposed simulation model reproduces well the experimental data and is useful for predicting and optimizing the electromechanical characteristics of highly stretchable fiber strain sensors based on CNT/polymer composites.

Highly Efficient Thin-Film Transistor via Cross-Linking of 1T Edge Functional 2H Molybdenum Disulfides.

Thin-film transistors (TFTs) have received great attention for their use in lightweight, large area, and wearable devices. However, low crystalline materials and inhomogeneous film formation limit the realization of high-quality electrical properties for channels in commercial TFTs, especially for flexible electronics. Here, we report a field-effect TFT fabricated via cross-linking of edge-1T basal-2H MoS2 sheets that are prepared by edge functional exfoliation of bulk MoS2 with soft organic exfoliation reagents. For edge functional exfoliation, the electrophilic 4-carboxy-benzenediazonium used as the soft organic reagent attacks the nucleophilic thiolates exposed at the edge of the bulk MoS2 with the help of an amine catalyst, resulting in 1T edge-functional HOOC-benzene-2H basal MoS2 nanosheets (e-MoS2). The cross-linking via hydrogen bonding of the negatively charged HOOC of the e-MoS2 sheets with the help of a cationic polymer, polydiallyldimethylammonium chloride, results in a good film formation for a channel of the solution processing TFT. The TFT exhibits an extremely high mobility of 170 cm2/(V s) at 1 V (on/off ratio of 106) on SiO2/Si substrate and also a high mobility of 36.34 cm2/(V s) (on/off ratio of 103) on PDMS/PET substrate.

Chemically modulated graphene quantum dot for tuning the photoluminescence as novel sensory probe.

A band gap tuning of environmental-friendly graphene quantum dot (GQD) becomes a keen interest for novel applications such as photoluminescence (PL) sensor. Here, for tuning the band gap of GQD, a hexafluorohydroxypropanyl benzene (HFHPB) group acted as a receptor of a chemical warfare agent was chemically attached on the GQD via the diazonium coupling reaction of HFHPB diazonium salt, providing new HFHPB-GQD material. With a help of the electron withdrawing HFHPB group, the energy band gap of the HFHPB-GQD was widened and its PL decay life time decreased. As designed, after addition of dimethyl methyl phosphonate (DMMP), the PL intensity of HFHPB-GQD sensor sharply increased up to approximately 200% through a hydrogen bond with DMMP. The fast response and short recovery time was proven by quartz crystal microbalance (QCM) analysis. This HFHPB-GQD sensor shows highly sensitive to DMMP in comparison with GQD sensor without HFHPB and graphene. In addition, the HFHPB-GQD sensor showed high selectivity only to the phosphonate functional group among many other analytes and also stable enough for real device applications. Thus, the tuning of the band gap of the photoluminescent GQDs may open up new promising strategies for the molecular detection of target substrates.

Tunable Sub-nanopores of Graphene Flake Interlayers with Conductive Molecular Linkers for Supercapacitors.

Although there are numerous reports of high performance supercapacitors with porous graphene, there are few reports to control the interlayer gap between graphene sheets with conductive molecular linkers (or molecular pillars) through a π-conjugated chemical carbon-carbon bond that can maintain high conductivity, which can explain the enhanced capacitive effect of supercapacitor mechanism about accessibility of electrolyte ions. For this, we designed molecularly gap-controlled reduced graphene oxides (rGOs) via diazotization of three different phenyl, biphenyl, and para-terphenyl bis-diazonium salts (BD1-3). The graphene interlayer sub-nanopores of rGO-BD1-3 are 0.49, 0.7, and 0.96 nm, respectively. Surprisingly, the rGO-BD2 0.7 nm gap shows the highest capacitance in 1 M TEABF4 having 0.68 nm size of cation and 6 M KOH having 0.6 nm size of hydrated cation. The maximum energy density and power density of the rGO-BD2 were 129.67 W h kg(-1) and 30.3 kW kg(-1), respectively, demonstrating clearly that the optimized sub-nanopore of the rGO-BDs corresponding to the electrolyte ion size resulted in the best capacitive performance.

Flexible and Stretchable Optoelectronic Devices using Silver Nanowires and Graphene.

Many studies have accompanied the emergence of a great interest in flexible or/and stretchable devices for new applications in wearable and futuristic technology, including human-interface devices, robotic skin, and biometric devices, and in optoelectronic devices. Especially, new nanodimensional materials enable flexibility or stretchability to be brought based on their dimensionality. Here, the emerging field of flexible devices is briefly introduced using silver nanowires and graphene, which are famous nanomaterials for the use of transparent conductive electrodes, as examples, and their unique functions originating from the intrinsic property of these nanomaterials are highlighted. It is thought that this work will evoke more interest and idea exchanges in this emerging field and hopefully can trigger a breakthrough on a new type of optoelectronics and optogenetic devices in the near future.

Moving beyond flexible to stretchable conductive electrodes using metal nanowires and graphenes.

Stretchable and/or flexible electrodes and their associated electronic devices have attracted great interest because of their possible applications in high-end technologies such as lightweight, large area, wearable, and biointegrated devices. In particular, metal nanowires and graphene derivatives are chosen for electrodes because they show low resistance and high mechanical stability. Here, we review stretchable and flexible soft electrodes by discussing in depth the intrinsic properties of metal NWs and graphenes that are driven by their dimensionality. We investigate these properties with respect to electronics, optics, and mechanics from a chemistry perspective and discuss currently unsolved issues, such as how to maintain high conductivity and simultaneous high mechanical stability. Possible applications of stretchable and/or flexible electrodes using these nanodimensional materials are summarized at the end of this review.

Highly Stretchable and Conductive Silver Nanoparticle Embedded Graphene Flake Electrode Prepared by In situ Dual Reduction Reaction.

The emergence of stretchable devices that combine with conductive properties offers new exciting opportunities for wearable applications. Here, a novel, convenient and inexpensive solution process was demonstrated to prepare in situ silver (Ag) or platinum (Pt) nanoparticles (NPs)-embedded rGO hybrid materials using formic acid duality in the presence of AgNO3 or H2PtCl6 at low temperature. The reduction duality of the formic acid can convert graphene oxide (GO) to rGO and simultaneously deposit the positively charged metal ion to metal NP on rGO while the formic acid itself is converted to a CO2 evolving gas that is eco-friendly. The AgNP-embedded rGO hybrid electrode on an elastomeric substrate exhibited superior stretchable properties including a maximum conductivity of 3012 S cm(-1) (at 0 % strain) and 322.8 S cm(-1) (at 35 % strain). Its fabrication process using a printing method is scalable. Surprisingly, the electrode can survive even in continuous stretching cycles.

High mechanical and tribological stability of an elastic ultrathin overcoating layer for flexible silver nanowire films.

A novel, nanoscale, thickness-controlled, elastic graphene oxide-polydiallyldimethylammonium chloride (GO-PDDA) film using a layer-by-layer technique on silver nanowires and a flexible substrate is reported. Micro- and nanoscale wear and flexibility depending on the thickness and/or elastic nature of the overcoating layer demonstrate high mechanical stability with the PDDA inserted overcoating layer.

An electrolyte-free flexible electrochromic device using electrostatically strong graphene quantum dot-viologen nanocomposites.

A strong electrostatic MV(2+) -GQD nanocomposite provides an electrolyte-free flexible electrochromic device wih high durability. The positively charged MV(2+) and negatively charged GQD are strongly stabilized by non-covalent intermolecular forces (e.g., electrostatic interactions, π-π stacking interactions, and cation-π electron interactions), eliminating the need for an electrolyte. An electrolyte-free flexible electrochromic device fabricated from the GQD-supported MV(2+) exhibits stable performance under mechanical and thermal stresses.

Facile preparation of an n-type reduced graphene oxide field effect transistor at room temperature.

We introduce a facile method to prepare an n-type reduced graphene oxide field effect transistor at room temperature via a typical Benkeser reduction using lithium and ethylenediamine.

Highly bendable, conductive, and transparent film by an enhanced adhesion of silver nanowires.

Recently, silver nanowires (AgNWs) have attracted considerable interest for their potential application in flexible transparent conductive films (TCFs). One challenge for the commercialization of AgNW-based TCFs is the low conductivity and stability caused by the weak adhesion forces between the AgNWs and the substrate. Here, we report a highly bendable, conductive, and transparent AgNW film, which consists of an underlying poly(diallyldimethyl-ammonium chloride) (PDDA) and AgNW composite bottom layer and a top layer-by-layer (LbL) assembled graphene oxide (GO) and PDDA overcoating layer (OCL). We demonstrated that PDDA could increase the adhesion between the AgNW and the substrate to form a uniform AgNW network and could also serve to improve the stability of the GO OCL. Hence, a highly bendable, conductive, and transparent AgNW-PDDA-GO composite TCF on a poly(ethylene terephthalate) (PET) substrate with Rs ≈ 10 Ω/sq and T ≈ 91% could be made by an all-solution processable method at room temperature. In addition, our AgNW-PDDA-GO composite TCF is stable without degradation after exposure to H2S gas or sonication.