Hydrogel‐Enabled Transfer‐Printing of Conducting Polymer Films for Soft Organic Bioelectronics

The use of conducting polymers such as poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) for the development of soft organic bioelectronic devices, such as organic electrochemical transistors (OECTs), is rapidly increasing. However, directly manipulating conducting polymer thin films on soft substrates remains challenging, which hinders the development of conformable organic bioelectronic devices. A facile transfer‐printing of conducting polymer thin films from conventional rigid substrates to flexible substrates offers an alternative solution. In this work, it is reported that PEDOT:PSS thin films on glass substrates, once mixed with surfactants, can be delaminated with hydrogels and thereafter be transferred to soft substrates without any further treatments. The proposed method allows easy, fast, and reliable transferring of patterned PEDOT:PSS thin films from glass substrates onto various soft substrates, facilitating their application in soft organic bioelectronics. By taking advantage of this method, skin‐attachable tattoo‐OECTs are demonstrated, relevant for conformable, imperceptible, and wearable organic biosensing.     

Optical Properties of Hybrid Organic‐Inorganic Materials and their Applications

Research on hybrid inorganic‐organic materials has experienced an explosive growth since the 1980s, with the expansion of soft inorganic chemistry based processes. Indeed, mild synthetic conditions, low processing temperatures provided by “chimie douce” and the versatility of the colloidal state allow for the mixing of the organic and inorganic components at the nanometer scale in virtually any ratio to produce the so called hybrid materials. Today a high degree of control over both composition and nanostructure of these hybrids can be achieved allowing tunable structure‐property relationships. This, in turn, makes it possible to tailor and fine‐tune many properties (mechanical, optical, electronic, thermal, chemical…) in very broad ranges, and to design specific multifunctional systems for applications. In particular, the field of “Hybrid‐Optics” has been very productive not only scientifically but also in terms of applications. Indeed, numerous optical devices based on hybrids are already in, or very close, to the market. This review describes most of the recent advances performed in this field. Emphasis will be given to luminescent, photochromic, NLO and plasmonic properties. As an outlook we show that the controlled coupling between plasmonics and luminescence is opening a land of opportunities in the field of “Hybrid‐Optics”.     

Multimodal Magneto‐Plasmonic Nanoclusters for Biomedical Applications

Multimodal nanostructures can help solve many problems in the biomedical field including sensitive molecular imaging, highly specific therapy, and early cancer detection. However, the synthesis of densely packed, multicomponent nanostructures with multimodal functionality represents a significant challenge. Here, a new type of hybrid magneto‐plasmonic nanoparticles is developed using an oil‐in‐water microemulsion method. The nanostructures are synthetized by self‐assembly of primary 6 nm iron oxide core‐gold shell particles resulting into densely packed spherical nanoclusters. The dense packing of primary particles does not change their superparamagnetic behavior; however, the close proximity of the constituent particles in the nanocluster leads to strong near‐infrared (NIR) plasmon resonances. The synthesis is optimized to eliminate nanocluster cytotoxicity. Immunotargeted nanoclusters are also developed using directional conjugation chemistry through the Fc antibody moiety, leaving the Fab antigen recognizing region available for targeting. Cancer cells labeled with immunotargeted nanoclusters produce a strong photoacoustic signal in the NIR that is optimum for tissue imaging. Furthermore, the labeled cells can be efficiently captured using an external magnetic field. The biocompatible magneto‐plasmonic nanoparticles can make a significant impact in development of point‐of‐care assays for detection of circulating tumor cells, as well as in cell therapy with magnetic cell guidance and imaging monitoring.     

Fabrication of CdSe‐Nanofibers with Potential for Biomedical Applications

The design and synthesis of nanostructured functional hybrid biomaterials are essential for the next generation of advanced diagnostics and the treatment of disease. A simple route to fabricate semiconductor nanofibers by self‐assembled, elastin‐like polymer (ELP)‐templated semiconductor nanoparticles is reported. Core–shell nanostructures of CdSe nanoparticles with a shell of ELPs are used as building blocks to fabricate functional one‐dimensional (1D) nanostructures. The CdSe particles are generated in situ within the ELP matrix at room temperature. The ELP controls the size and the size‐distribution of the CdSe nanoparticles in an aqueous medium and simultaneously directs the self‐assembly of core–shell building blocks into fibril architectures. It was found that the self‐assembly of core–shell building blocks into nanofibers is strongly dependent on the pH value of the medium. Results of cytotoxicity and antiproliferation of the CdSe‐ELP nanofibers demonstrate that the CdSe‐ELP does not exhibit any toxicity towards B14 cells. Moreover, these are found to be markedly capable of crossing the cell membrane of B14. In contrast, unmodified CdSe nanoparticles with ELPs cause a strong toxic response and reduction in the cell proliferation. This concept is valid for the fabrication of a variety of metallic and semiconductor 1D‐architectures. Therefore, it is believed that these could be used not only for biomedical purposes but for application in a wide range of advanced miniaturized devices.     

Plasma Enabled Conformal and Damage Free Encapsulation of Fragile Molecular Matter: from Surface‐Supported to On‐Device Nanostructures

Damage‐free encapsulation of molecular structures with functional nanolayers is crucial to protect nanodevices from environmental exposure. With nanoscale electronic, optoelectronic, photonic, sensing, and other nanodevices based on atomically thin and fragile organic matter shrinking in size, it becomes increasingly challenging to develop nanoencapsulation that is simultaneously conformal at atomic scale and does not damage fragile molecular networks, while delivering added device functionality. This work presents an effective, plasma‐enabled, potentially universal approach to produce highly conformal multifunctional organic films to encapsulate atomically thin graphene layers and metalorganic nanowires, without affecting their molecular structure and atomic bonding. Deposition of adamantane precursor and gentle remote plasma chemical vapor deposition are synergized to assemble molecular fragments and cage‐like building blocks and completely encapsulate not only the molecular structures, but also the growth substrates and device elements upon nanowire integration. The films are insulating, transparent, and conformal at sub‐nanometer scale even on near‐tip high‐curvature areas of high‐aspect‐ratio nanowires. The encapsulated structures are multifunctional and provide effective electric isolation, chemical and environmental protection, and transparency in the near‐UV–visible–near‐infrared range. This single‐step, solvent‐free remote‐plasma approach preserves and guides molecular building blocks thus opening new avenues for precise, atomically conformal nanofabrication of fragile nanoscale matter with multiple functionalities.     

Solid‐State Electrode Materials with Ionic‐Liquid Properties for Energy Storage: the Lithium Solid‐State Ionic‐Liquid Concept.

Herein, the novel concept of a solid‐state electrode materials with ionic‐liquid (IL) properties is presented. These composite materials are a mixture of electroactive matter, an electronic conductor, a solid‐state ionic conductor and a polymeric binder. The approach of a solid‐state ionic conductor combines the high safety of an IL with the nanoconfinement of such a liquid in a mesoporous silica framework, an ionogel, thus leading to a solid with liquid‐like ionic properties. The same ionic conductor is also used as a solid‐state separator to evaluate the properties of our solid‐state electrode materials in all‐solid‐state batteries. Such a concept of a solid‐state electrode material contributes to addressing the challenge of energy storage, which is one of the major challenges of the 21^st century. The ionogel, along with its processability, allows a single‐step preparation of the assembly of the solid‐state electrode and solid‐electrolyte separator and can be applied without specific adaptation to present, thick electrodes prepared by the widespread tape‐casting technique. The filling of the electrode porosity by an ionogel is shown by elemental mapping using scanning electron microscopy, and is subsequently confirmed by electrochemical measurements. The ionogel approach is successfully applied without specific adaptation to two state‐of‐the‐art, positive electroactive materials developed for future‐generation lithium‐ion batteries, namely LiFePO₄ and LiNi_1/3Mn_1/3Co_1/3O₂.     

Synthetic Strategies for Hybrid Materials to Improve Properties for Optoelectronic Applications

We report, for the first time to the best of our knowledge, a systematic study to relate the laser action from BODIPY dyes, doped into monolithic hybrid matrices, with the synthetic protocols of the final materials prepared via sol‐gel. To this aim, the influence of both the hydrolysis time, increased in a controlled way, and the nature of the neutralization agent (pyridine, 3‐amino‐propyltriethoxy‐silane (APS), N‐[3‐(trimethoxysilyl)propyl]‐ethylene diamine (TSPDA), and N¹‐[3‐(trimethoxysilyl)propyl]‐ diethylene triamine (TSPTA) on the laser action of PM567, incorporated into hybrid matrices based on copolymers of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA), with methyltriethoxysilane (TRIEOS) as inorganic precursor, was analyzed. The presence of the amine‐modified silane TSPDA as neutralization agent, which is able at the same time to be anchored to the inorganic network enhancing the inorganic‐organic compatibility through the matrix interphase, and utilization of hydrolysis times lower than 10 minutes, increased significantly the lasing efficiency and photostability of dye. The extension of this study to the laser behavior of BODIPY dyes embedded in other different hybrid materials based on hydrolyzed‐condensed copolymers of MMA with 3‐(trimethoxysilyl)propyl methacrylate (TMSPMA) in a 1/1 volumetric proportion, validates the generalization of the above conclusions, which provide guides for the optimization of the synthesis of organic‐inorganic hybrid materials with optoelectronic innovative applications independently of their composition.     

Light‐Guiding Biomaterials for Biomedical Applications

Optical techniques used in medical diagnosis, surgery, and therapy require efficient and flexible delivery of light from light sources to target tissues. While this need is currently fulfilled by glass and plastic optical fibers, recent emergence of biointegrated approaches, such as optogenetics and implanted devices, calls for novel waveguides with certain biophysical and biocompatible properties and desirable shapes beyond what the conventional optical fibers can offer. To this end, exploratory efforts have begun to harness various transparent biomaterials to develop waveguides that can serve existing applications better and enable new applications in future photomedicine. Here, the recent progress in this new area of research for developing biomaterial‐based optical waveguides is reviewed. It begins with a survey of biological light‐guiding structures found in plants and animals, a source of inspiration for biomaterial photonics engineering. The review then describes natural and synthetic polymers and hydrogels that offer appropriate optical properties, biocompatibility, biodegradability, and mechanical flexibility have been exploited for light‐guiding applications. Finally, perspectives on biomedical applications that may benefit from the unique properties and functionalities of light‐guiding biomaterials are discussed briefly.     

Structurally Stable Manganese Alkoxide Films Grown by Hybrid Molecular Layer Deposition for Electrochemical Applications

Hybrid molecular layer deposition (MLD) has significant potential for the creation of ultrathin electrochemically active materials, due to its ability to combine organic and inorganic species to modulate film properties. However, only a limited number of hybrid MLD processes are demonstrated with electrochemically relevant elements, such as manganese. Here, a “manganicone” manganese hybrid MLD chemistry is developed using the precursors bis(ethylcyclopentadienyl)manganese and ethylene glycol. The resulting manganese alkoxide coordination networks are shown to have many interesting properties, including the ability to seamlessly fill high aspect ratio vias and the chemical conversion into manganese carboxylate in air over several hours at room temperature. Linear, self‐saturating growth is reported. Importantly, hybrid manganicone films annealed to 480 °C in air demonstrate a greater stability to restructuring during electrochemical testing than their inorganic counterparts grown by atomic layer deposition, without reducing the activity of the reactive sites on the manganese surface. Thus, hybrid manganese films grown by MLD have significant promise for use as catalysts for the oxygen evolution reaction and as electrodes in thin film batteries.     

High‐Performance Hybrid Supercapacitor Enabled by a High‐Rate Si‐based Anode

A hybrid supercapacitor constructed of a Si‐based anode and a porous carbon cathode is demonstrated with both high power and energy densities. Boron‐doping is employed to improve the rate capability of the Si‐based anode (B‐Si/SiO₂/C). At a high current density of 6.4 A/g, B‐Si/SiO₂/C delivers a capacity of 685 mAh/g, 2.4 times that of the undoped Si/SiO₂/C. Benefiting from the high rate performance along with low working voltage, high capacity, and good cycling stability of B‐Si/SiO₂/C, the hybrid supercapacitor exhibits a high energy density of 128 Wh/kg at 1229 W/kg. Even when power density increases to the level of a conventional supercapacitor (9704 W/kg), 89 Wh/kg can be obtained, the highest values of any hybrid supercapacitor to date. Long cycling life (capacity retention of 70% after 6000 cycles) and low self‐discharge rate (voltage retention of 82% after 50 hours) are also achieved. This work opens an avenue for development of high‐performance hybrid supercapacitors using high‐performance Si‐based anodes.     

Network Structure Modification‐Enabled Hybrid Polymer Dielectric Film with Zirconia for the Stretchable Transistor Applications

Stretchable electronic devices should be enabled by the smart design of materials and architectures because their commercialization is limited by the tradeoff between stretchability and electrical performance limits. In this study, thin‐film transistors are fabricated using strategies that combine the unit process of a novel hybrid gate insulator and low‐temperature indium gallium tin oxide (IGTO) channel layer and a stress‐relief substrate structure. Novel hybrid dielectric films are synthesized and their molecular structural configurations are analyzed. These films consist of a polymer [poly(4‐vinylphenol‐co‐methylmethacrylate)], cross‐linkers having different binding structures [1,6‐bis(trimethoxysilyl)hexane (BTMSH), dodecyltrimethoxysilane, and poly(melamine‐co‐formaldehyde)], and an inorganic zirconia component (ZrO_x). The hybrid film with BTMSH cross‐linker and 0.2 M ZrO_x exhibits excellent insulating properties as well as mechanical stretchability. IGTO transistors fabricated on polyimide‐coated glass substrates are transferred to the rubber substrate to offer stretchability of the transistor pixelated thin‐film transistors. IGTO transistors fabricated on stretchable substrates using these strategies show promising electrical performance and mechanical durability. After 200 stretchability test cycles under uniaxial elongation of approximately 300%, the IGTO transistor still retains a high carrier mobility of 21.7 cm² V^?1 s^?1, a low sub‐threshold gate swing of 0.68 V decade^?1 and a high I_ON/OFF ratio of 2.0 × 10⁷.     

Ligand‐Driven Wavelength‐Tunable and Ultra‐Broadband Infrared Luminescence in Single‐Ion‐Doped Transparent Hybrid Materials

Here, tuning of the optical properties of emission centers by tailoring the ligand fields is investigated. Experimentally, it is demonstrated that Ni²⁺ can act as a single emission species in multiple octahedral local environments. Nanocrystal‐embedded hybrid materials are employed as hosts in order to take advantage of their convenience in local environment design for practical applications. Novel composite gain materials with high transparence are successfully made, and show interesting wavelength‐tunable and ultra‐broadband infrared luminescence covering the whole near‐infrared region from 1 100 to 1 800 nm. The infrared luminescence peak positions can be finely tuned from 1 300 to 1 450 and to 1 570 nm, with the largest full width at half maximum being about 400 nm and covering the telecommunication bands at 1 200–1 500 nm. According to the results of characterization, the unusual luminescence, interestingly, originates from Ni²⁺ in nanocrystals and the doping efficiency of Ni²⁺ is surprisingly high. The results demonstrate that the method presented may be an effective way to fabricate multifunctional light sources with various fundamental multifunctional applications from efficient broadband optical amplifiers to bio‐imaging.     

Polyfluorene Derivatives are High‐Performance Organic Hole‐Transporting Materials for Inorganic−Organic Hybrid Perovskite Solar Cells

Photovoltaics based on organic?inorganic perovskites offer new promise to address the contemporary energy and environmental issues. These solar cells have so far largely relied on small‐molecule hole transport materials such as spiro‐OMeTAD, which commonly suffer from high cost and low mobility. In principle, polyfluorene copolymers can be an ideal alternative to spiro‐OMeTAD, given their low price, high hole mobility and good processability, but this potential has not been explored. Herein, polyfluorene derived polymers‐TFB and PFB, which contain fluorine and arylamine groups, are demonstrated and can indeed rival or even outperform spiro‐OMeTAD as efficient hole‐conducting materials for perovskite solar cells. In particular, under the one‐step perovskite deposition condition, TFB achieves a 10.92% power conversion efficiency that is considerably higher than that with spiro‐OMeTAD (9.78%), while using the two‐step perovskite deposition method, about 13% efficient solar cells with TFB (12.80%) and spiro‐OMeTAD (13.58%) are delivered. Photo­luminescence reveals the efficient hole extraction and diffusion at the interface between CH₃NH₃PbI₃ and the hole conducting polymer. Impedance spectroscopy uncovers the higher electrical conductivity and lower series resistance than spiro‐OMeTAD, accounting for the significantly higher fill factor, photocurrent and open‐circuit voltage of the TFB‐derived cells than with spiro‐MeOTAD.     

Surface‐Confined Atom Transfer Radical Polymerization from Sacrificial Mesoporous Silica Nanospheres for Preparing Mesoporous Polymer/Carbon Nanospheres with Faithful Shape Replication: Functional Mesoporous Materials

A facile approach for the preparation of mesoporous polymer nanospheres (MPN) and mesoporous carbon nanospheres (MCN) with complete shape retention based on surface‐confined atom transfer radical polymerization of various methacrylate monomers from in situ generated initiator‐modified hard silica nanospheres template is developed. This approach yields mesoporous silica‐polymer hybrid nanospheres (MSPN) with mesopores that are uniformly filled with covalently attached well‐defined poly(methacrylate)s. The silica frameworks are subsequently etched, resulting in MPN. Pyrolysis of MSPN and subsequent removal of silica template resulted in the production of MCN. They retain the size, shape, and mesoporous ordering of the silica template nanospheres. Gel permeation chromatography analysis of the silica free polymers reveals that they have controlled molecular weights and low polydispersities (PDIs). Kinetics studies reveal that the molecular weight of the grafted polymer increases linearly with time, maintaining low PDIs, indicating the living nature of the polymerization. The mesoporous polymer material is found to have low dielectric constant, which paves the way for their use as low‐dielectric constant materials in microelectronics. This approach allows fabrication of functional MPN using functional comonomers, which are successfully used for the synthesis of “clickable” mesoporous polymer nanospheres, removal of ionic contaminates through anion exchange, and glucose sensing.     

Fractal Inorganic−Organic Interfaces in Hybrid Membranes for Efficient Proton Transport

A facile method for preparing highly conductive hybrid organic?inorganic membranes is reported. These membranes are synthesized using an electrospinning process with a sol?gel‐based solution containing PVDF?HFP (polyvinylidenefluoride‐hexafluoropropylene), functionalized or not functionalized silicon alkoxides, and additives. Proton conduction measurements highlight that these hybrid membranes exhibit conductivity value of 101 mS/cm at 120 °C under 80% RH (relative humidity), comparable to the best Nafion measured under the same conditions. These membranes have a proton conductivity‐humidity variation close to Nafion and a modulus value higher than that for Nafion above 80 °C. Their proton conductivity value is about 15 mS/cm under 50% RH, and it constitutes one of the highest values reported. These interesting properties are related to the microstructure of the electrospun membranes that have been characterized using field emission scanning electron microscopy (FE‐SEM) and small angle neutron scattering (SANS). The electrospun membranes are made composed of a bundle of fibers surrounded by a functionalized silica network. The bundle of fibers corresponds to the assembly of small polymer fibers surrounded by small anisotropic functionalized silica domains. Coupling the reactive chemistry of the sol–gel‐based process with electrospinning allows the design of hybrid membranes with fractal hydrophobic/hydrophilic interfaces exhibiting different length scales.     

Enhanced Variable Stiffness and Variable Stretchability Enabled by Phase‐Changing Particulate Additives

A novel phase‐changing particulate that amplifies a composite's modulus change in response to thermal stimulus is introduced. This particulate additive consists of a low melting point alloy (Field's metal; FM) formed into microparticles using a facile fabrication method, which enables its incorporation into polymer matrices using simple composite manufacturing processes. The effect of the solid–liquid phase change of the FM particles is demonstrated in two host materials: a thermally responsive epoxy and a silicone elastomer. In the epoxy matrix, this thermal response manifests as an amplified change in flexural modulus when heated, which is highly desirable for stiffness‐changing move‐and‐hold applications. In the silicone matrix, the stretchability can be switched depending on the phase of the FM particles. This phenomenon allows the silicone to stretch and hold a strained configuration, and gives rise to mechanically programmable anisotropy through reshaping of the FM inclusions. FM particles present many opportunities where on‐demand tunable modulus is required, and is particularly relevant to soft robotics. Because the melting temperature of FM is near room temperature, triggering the phase change requires low power consumption. The utility of FM particle‐containing composites as variable stiffness and variable stretchability elements for soft robotic applications is demonstrated.     

Graphene‐Based Nanoporous Materials Assembled by Mediation of Polyoxometalate Nanoparticles

A kind of graphene‐based nanoporous material is prepared through assembling graphene sheets mediated through polyoxometalate nanoparticles. Owing to the strong interaction between graphene and polyoxometalate, 2D graphene sheets with honeycomb‐latticed carbon atoms could assemble into a porous structure, in which 3D polyoxometalate nanoparticles serve as the crosslinkers. Nitrogen and hydrogen sorption analysis reveal that the as‐prepared graphene‐based hybrid material possesses a specific surface area of 680 m² g^?1 and a hydrogen uptake volume of 0.8?1.3 wt%. Infrared spectrometry is used to probe the electron density changes of polyoxometalate particle in the redox‐cycle and to verify the interaction between graphene and polyoxometalate. The as‐prepared graphene‐based materials are further characterized by Raman spectroscopy, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy.     

Covalently Tethered Polyoxometalate–Pyrene Hybrids for Noncovalent Sidewall Functionalization of Single‐Walled Carbon Nanotubes as High‐Performance Anode Material

A covalently tethered polyoxometalate (POM)–pyrene hybrid (Py–SiW₁₁) is utilized for the noncovalent functionalization of single‐walled carbon nanotubes (SWNTs). The resulting SWNTs/Py–SiW₁₁ nanocomposite shows that both SiW₁₁ and pyrene moieties could interact with SWNTs without causing any chemical decomposition. When used as anode material in lithium‐ion batteries, the SWNTs/Py–SiW₁₁ nanocomposite exhibits higher discharge capacities, and better rate capacity and cycling stability than the individual components. When the current density is 0.5 mA cm^?2, the nanocomposite exhibits the initial discharge capacity of 1569.8 mAh g^?1, and a high discharge capacity of 580 mAh g^?1 for up to 100 cycles.     

Compact and Light Supercapacitor Electrodes from a Surface‐Only Solid by Opened Carbon Nanotubes with 2 200 m2 g−1 Surface Area

An approach is presented to make a “surface‐only solid” with a surface area of 2 240 m² g^?1 (1 310 m² cm^?3), corresponding to 85% of the atoms constituting a surface, by opening single‐walled carbon nanotube forests and solids via controlled oxidation. The controllability of the approach is demonstrated by tailoring the hole size to match the guest molecule, for example, nitrogen, fullerene, or solvated ions. These features make the surface‐only solid an ideal vessel for material and energy storage, as demonstrated by its use for electrodes to realize a light and compact supercapacitor with high energy (24.7 W h kg^?1) and power (98.9 kW kg^?1) densities, exceeding those of activated carbon (16.9 W h kg^?1 and 35.7 kW kg^?1).