In Situ Polymerization of Dopamine on Graphene Framework for Charge Storage Applications

Polydopamine, a functional coating material, is redox active as cathode materials for both Li‐ and Na‐ion batteries or hybrid capacitors. Here, a polydopamine coating onto 3D graphene framework is introduced through a simple hydrothermal process, during which graphene oxide serves not only as an oxidant for assisting the polymerization of dopamine, but also as a template for the conformal growth of polydopamine. High‐density films are fabricated by compressing the polydopamine‐coated graphene aerogels, which can be directly used as free‐standing and flexible cathodes in both Li‐ and Na‐cells. The compact electrodes deliver high capacities of ≈230 mAh g⁻¹ in Li‐cells and ≈211 mAh g⁻¹ in Na‐cells based on the total mass of electrodes. These compact electrodes also exhibit exceptional cycling stability and high rate performance due to the unique structure in which polydopamine is uniformly coated on the 3D structured graphene.     

Micrometer‐Thick Graphene Oxide–Layered Double Hydroxide Nacre‐Inspired Coatings and Their Properties

Robust, functional, and flame retardant coatings are attractive in various fields such as building construction, food packaging, electronics encapsulation, and so on. Here, strong, colorful, and fire‐retardant micrometer‐thick hybrid coatings are reported, which can be constructed via an enhanced layer‐by‐layer assembly of graphene oxide (GO) nanosheets and layered double hydroxide (LDH) nanoplatelets. The fabricated GO–LDH hybrid coatings show uniform nacre‐like layered structures that endow them good mechanic properties with Young's modulus of ≈18 GPa and hardness of ≈0.68 GPa. In addition, the GO–LDH hybrid coatings exhibit nacre‐like iridescence and attractive flame retardancy as well due to their well‐defined 2D microstructures. This kind of nacre‐inspired GO–LDH hybrid thick coatings will be applied in various fields in future due to their high strength and multifunctionalities.     

Using Graphene Oxide to Enhance the Barrier Properties of Poly(lactic acid) Film

The ultra‐thin (polyethyleneimine/graphene oxide)_n [(PEI/GO)_n]multilayer films on poly(lactic acid) (PLA) were constructed via the layer‐by‐layer assembly. Here, the electrostatic interactions between PEI and GO were used to obtain the nanoscale composite membrane of (PEI/GO)_n on the surface of PLA film. With the number of assembling layers increased, the oxygen permeability (PO₂) of PLA film decreased substantially. As a 0.06 wt% GO solution was used with only four layers, the PO₂ decreased from 53.8 to 0.377 × 10^?4 cm³/m²/d/Pa, only 0.7% of the original PLA film. At the same time, the coated PLA film also presented a good transparency and better mechanical properties. It is a novel way to use GO on biodegradable packaging materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Delivery of a Therapeutic Protein for Bone Regeneration from a Substrate Coated with Graphene Oxide

The therapeutic efficacy of drugs often depends on the drug delivery carrier. For efficient delivery of therapeutic proteins, delivery carriers should enable the loading of large doses, sustained release, and retention of the bioactivity of the therapeutic proteins. Here, it is demonstrated that graphene oxide (GO) is an efficient carrier for delivery of therapeutic proteins. Titanium (Ti) substrates are coated with GO through layer‐by‐layer assembly of positively (GO‐NH₃⁺) and negatively (GO‐COO^?) charged GO sheets. Subsequently, a therapeutic protein (bone morphogenetic protein‐2, BMP‐2) is loaded on the GO‐coated Ti substrate with the outermost coating layer of GO‐COO^?(Ti/GO‐). The GO coating on Ti substrate enables loading of large doses and the sustained release of BMP‐2 with preservation of the structure and bioactivity of the drug. The extent of in vitro osteogenic differentiation of human bone marrow‐derived mesenchymal stem cells is higher when they are cultured on Ti/GO‐ carrying BMP‐2 than when they are cultured on Ti with BMP‐2. Eight weeks after implantation in mouse models of calvarial defects, the Ti/GO‐/BMP‐2 implants show more robust new bone formation compared with Ti, Ti/GO‐, or Ti/BMP‐2 implants. Therefore, GO is an effective carrier for the controlled delivery of therapeutic proteins, such as BMP‐2, which promotes osteointegration of orthopedic or dental Ti implants.     

Non‐Volatile ReRAM Devices Based on Self‐Assembled Multilayers of Modified Graphene Oxide 2D Nanosheets

2D nanomaterials have been actively utilized in non‐volatile resistive switching random access memory (ReRAM) devices due to their high flexibility, 3D‐stacking capability, simple structure, transparency, easy fabrication, and low cost. Herein, it demonstrates re‐writable, bistable, transparent, and flexible solution‐processed crossbar ReRAM devices utilizing graphene oxide (GO) based multilayers as active dielectric layers. The devices employ single‐ or multi‐component‐based multilayers composed of positively charged GO (N‐GO(+) or NS‐GO(+)) with/without negatively charged GO(‐) using layer‐by‐layer assembly method, sandwiched between Al bottom and Au top electrodes. The device based on the multi‐component active layer Au/[N‐GO(+)/GO(‐)]_n/Al/PES shows higher ON/OFF ratio of ≈10⁵ with switching voltage of ?1.9 V and higher retention stability (≈10⁴ s), whereas the device based on single component (Au/[N‐GO(+)]_n/Al/PES) shows ≈10³ ON/OFF ratio at ±3.5 V switching voltage. The superior ReRAM properties of the multi‐component‐based device are attributed to a higher coating surface roughness. The Au/[N‐GO(+)/GO(–)]_n/Al/PES device prepared from lower GO concentration (0.01%) exhibits higher ON/OFF ratio (≈10⁹) at switching voltage of ±2.0 V. However, better stability is achieved by increasing the concentration from 0.01% to 0.05% of all GO‐based solutions. It is found that the devices containing MnO₂ in the dielectric layer do not improve the ReRAM performance.     

Characterization of dense arrays of chemiresistor vapor sensors with submicrometer features and patterned nanoparticle interface layers

The performance of arrays of small, densely integrated chemiresistor (CR) vapor sensors with electron-beam patterned interface layers of thiolate-monolayer-protected gold nanoparticles (MPNs) is explored. Each CR in the array consists of a 100-μm(2) interdigital electrode separated from adjacent devices by 4 μm. Initial studies involved four separate arrays, each containing four CRs coated with one of four different MPNs, which were calibrated with five vapors before and after MPN-film patterning. MPNs derived from n-octanethiol (C8), 4-(phenylethynyl)-benzenethiol (DPA), 6-phenoxyhexane-1-thiol (OPH), and methyl-6-mercaptohexanoate (HME) were tested. Parallel calibrations of MPN-coated thickness-shear-mode resonators (TSMR) were used to derive partition coefficients of unpatterned films and to assess transducer-dependent factors affecting responses. A 600-μm(2) 4-CR array with four different patterned MPN interface layers, in which the MPN derived from 7-hydroxy-7,7-bis(trifluoro-methyl)heptane-1-thiol (HFA) was substituted for HME, was then characterized. This is the smallest multi-MPN array yet reported. Reductions in the diversity of the collective response patterns are observed with the patterned films, but projected vapor discrimination rates remain high. The use of such arrays as ultralow-dead-volume detectors in microscale gas chromatographic analyzers is discussed.     

Effects on Oxygen‐barrier Properties of Pretreating Paperboard with a Starch–Poly(Vinyl Alcohol) Blend before Polyethylene Extrusion

Polyethylene (PE) extrusion coating was performed on paperboard pre‐coated with water‐borne barrier coatings based on starch–poly(vinyl) (PVOH)–plasticizer blends in order to investigate that how the addition of a plasticizer to the pre‐coating affects the oxygen‐barrier properties of the board after PE extrusion coating. The plasticizers used were glycerol, polyethylene glycol (PEG) and citric acid (CA). Photomicrographs showed that the barrier coating layers were rather smooth, but defects were observed in the starch–PVOH layers when a plasticizer was added. Starch–PVOH layers had oxygen‐barrier properties similar to those of pure PVOH without plasticizers. When a sufficient number of layers (four layers) were applied to cover defects, the starch–PVOH layers containing CA showed oxygen transmission rate (OTR) values similar to those of starch–PVOH layers without plasticizer. The adhesion of PE to pre‐coated paperboard decreased when a plasticizer was added to the pre‐coating recipes. PE extrusion coating resulted in a reduction in the OTR in the case of pre‐coating formulations containing plasticizers. A lower OTR after polyethylene extrusion was observed with PEG as plasticizer than with CA as plasticizer. This could be explained by the increase in brittleness due to cross‐linking under the high temperature load during the extrusion process. Dynamic mechanical analysis of the films showed a substantial increase in storage modulus between 100°C and 200°C for CA‐containing starch–PVOH films. The contact angle of diiodomethane on the pre‐coating layer decreased when a plasticizer was added to the coating recipe indicating an increase in wetting of the PE melt. Addition of PEG to the pre‐coating led to a greater wetting than the addition of CA, and this may have sealed some defects in the pre‐coating leading to lower OTR values.     

Graphene‐Assisted Growth of Patterned Perovskite Films for Sensitive Light Detector and Optical Image Sensor Application

Controlled growth of high‐quality patterned perovskite films on a large scale is essentially required for the application of this class of materials in functional integrated devices and systems. Herein, graphene‐assisted hydrophilic–hydrophobic surface‐induced growth of Cs‐doped FAPbI₃ perovskite films with well‐patterned shapes by a one‐step spin‐coating process is developed. Such a facile fabrication technique is compatible with a range of spin‐coated perovskite materials, perovskite manufacturing processes, and substrates. By employing this growing method, controllable perovskite photodetector arrays are realized, which have not only prominent photoresponse properties with a responsivity and specific detectivity of 4.8 AW^?1 and 4.2 × 10¹² Jones, respectively, but also relatively small pixel‐to‐pixel variation. Moreover, the photodetectors array can function as an effective visible light image sensor with a decent spatial resolution. Holding the above merits, the proposed technique provides a convenient and effective pathway for large‐scale preparation of patterned perovskite films for multifunctional application purposes.     

A Comparison of the Cell Compatibility of Poly(ethyleneimine) with that of other Cationic Biopolymers Used in Applications at Biointerfaces

Poly(ethyleneimine) (PEI) is used as an initiating base layer or intermediate layer for layer‐by‐layer (LBL) technology. Since PEI is potentially cytotoxic in solution, it is necessary to investigate the influence of the physical properties of PEI layers on osteoblast cells. Therefore, the first aim of this study was to test the hypothesis that there is no statistically significant difference of cell adhesion, proliferation, and viability in response to nanometer thin polymer layers of PEI compared to other well‐known polymers. The second aim of this study was to test the hypothesis that the amine‐substituted dextran (aminodextran (AMD)) adheres well on Ti and can be used as a polymer coating in biomaterials applications. Titanium samples were coated with PEI, poly‐L ‐lysine (PLL), or AMD using dip coating. The polymer films were investigated with ellipsometry, atomic force microscopy, contact angle measurements, and X‐ray‐photoelectron spectroscopy (XPS). Cell adhesion, proliferation, and viability tests were carried out using osteoblast‐like cells (CAL‐72). Thin polymer layers below 10 nm layer thickness were found on the Ti surfaces. It was shown for the first time that base layers of PEI with nanometer thickness do not affect the bone cell reaction negatively. PEI, therefore, can be used as a functional base layer for LBL functionalization of metallic implants. AMD can be used in biomedical applications but does not adhere on titanium without an adhesion promoter.     

Synthesis of Large‐Area InSe Monolayers by Chemical Vapor Deposition

Recently, 2D materials of indium selenide (InSe) layers have attracted much attention from the scientific community due to their high mobility transport and fascinating physical properties. To date, reports on the synthesis of high‐quality and scalable InSe atomic films are limited. Here, a synthesis of InSe atomic layers by vapor phase selenization of In₂O₃ in a chemical vapor deposition (CVD) system, resulting in large‐area monolayer flakes or thin films, is reported. The atomic films are continuous and uniform over a large area of 1 × 1 cm², comprising of primarily InSe monolayers. Spectroscopic and microscopic measurements reveal the highly crystalline nature of the synthesized InSe monolayers. The ion‐gel‐gated field‐effect transistors based on CVD InSe monolayers exhibit n‐type channel behaviors, where the field effect electron mobility values can be up to ≈30 cm² V^?1 s^?1 along with an on/off current ratio, of >10⁴ at room temperature. In addition, the graphene can serve as a protection layer to prevent the oxidation between InSe and the ambient environment. Meanwhile, the synthesized InSe films can be transferred to arbitrary substrates, enabling the possibility of reassembly of various 2D materials into vertically stacked heterostructures, prompting research efforts to probe its characteristics and applications.     

Direct Optical Patterning of Quantum Dot Light-Emitting Diodes via In Situ Ligand Exchange

Precise patterning of quantum dot (QD) layers is an important prerequisite for fabricating QD light-emitting diode (QLED) displays and other optoelectronic devices. However, conventional patterning methods cannot simultaneously meet the stringent requirements of resolution, throughput, and uniformity of the pattern profile while maintaining a high photoluminescence quantum yield (PLQY) of the patterned QD layers. Here, a specially designed nanocrystal ink is introduced, “photopatternable emissive nanocrystals” (PENs), which satisfies these requirements. Photoacid generators in the PEN inks allow photoresist-free, high-resolution optical patterning of QDs through photochemical reactions and in situ ligand exchange in QD films. Various fluorescence and electroluminescence patterns with a feature size down to ≈1.5 µm are demonstrated using red, green, and blue PEN inks. The patterned QD films maintain ≈75% of original PLQY and the electroluminescence characteristics of the patterned QLEDs are comparable to thopse of non-patterned control devices. The patterning mechanism is elucidated by in-depth investigation of the photochemical transformations of the photoacid generators and changes in the optical properties of the QDs at each patterning step. This advanced patterning method provides a new way for additive manufacturing of integrated optoelectronic devices using colloidal QDs.     

Whey protein isolate coating on LDPE film as a novel oxygen barrier in the composite structure

To examine the feasibility of whey protein isolate (WPI) coating as an alternative oxygen barrier for food packaging, heat‐denatured aqueous solutions of WPI with various levels of glycerol as a plasticizer were applied on corona‐discharge‐treated low‐density polyethylene (LDPE) films. The resulting WPI‐coated LDPE films showed good appearance, flexibility and adhesion between the coating and the base film, when an appropriate amount of plasticizer was added to the coating formulations. WPI‐coated LDPE films showed significant decrease in oxygen permeability (OP) at low to intermediate relative humidity, with an Arrhenius behaviour and an activation energy of 50.26 kJ/mol. The OP of the coated films increased significantly with increasing relative humidity, showing an exponential function. Although the coated films showed a tendency to have less oxygen barrier and more glossy surfaces with increasing plasticizer content, differences in the OP and gloss values were not significant. Haze index and colour of the coated films were also little influenced by WPI coating and plasticizer content. The results suggest that whey protein isolate coating could work successfully as an oxygen barrier and have potential for replacing synthetic plastic oxygen‐barrier layers in many laminated food packaging structures. Copyright © 2004 John Wiley & Sons, Ltd.     

Fabrication of transparent conductive electrode film using thermal roll-imprinted Ag metal grid and coated conductive polymer

In this study, to fabricate a low-resistance and high optical transparent conductive electrode (TCE) film, the following steps were performed: the design and manufacture of an electroforming stamp mold, the fabrication of thermal-roll imprinted (TRI) poly-carbonate (PC) patterned films, the manufacture of high-conductivity and low-resistance Ag paste which was filled into patterned PC film using a doctor blade process and then coated with a thin film layer of conductive polymer by a spin coating process. As a result of these imprinting processes the PC films obtained a line width of 10 +/- 0.5 Mm, a channel length of 500 +/- 2 microm, and a pattern depth of 7.34 +/- 0.5 microm. After the Ag paste was used to fill part of the patterned film with conductive polymer coating, the following parameters were obtained: a sheet resistance of 9.65 Omega/sq, optical transparency values were 83.69% at a wavelength of 550 nm.     

ZnO Coated Anodic 1D TiO2 Nanotube Layers: Efficient Photo‐Electrochemical and Gas Sensing Heterojunction

The authors demonstrate, in this work, a fascinating synergism of a high surface area heterojunction between TiO₂ in the form of ordered 1D anodic nanotube layers of a high aspect ratio and ZnO coatings of different thicknesses, produced by atomic layer deposition. The ZnO coatings effectively passivate the defects within the TiO₂ nanotube walls and significantly improve their charge carrier separation. Upon the ultraviolet and visible light irradiation, with an increase of the ZnO coating thickness from 0.19 to 19 nm and an increase of the external potential from 0.4–2 V, yields up to 8‐fold enhancement of the photocurrent density. This enhancement translates into extremely high incident photon to current conversion efficiency of ≈95%, which is among the highest values reported in the literature for TiO₂ based nanostructures. In addition, the photoactive region is expanded to a broader range close to the visible spectral region, compared to the uncoated nanotube layers. Synergistic effect arising from ZnO coated TiO₂ nanotube layers also yields an improved ethanol sensing response, almost 11‐fold compared to the uncoated nanotube layers. The design of the high‐area 1D heterojunction, presented here, opens pathways for the light‐ and gas‐assisted applications in photocatalysis, water splitting, sensors, and so on.

     

Conformal Coating of Co/N‐Doped Carbon Layers into Mesoporous Silica for Highly Efficient Catalytic Dehydrogenation–Hydrogenation Tandem Reactions

To maximize the utilizing efficiency of cobalt (Co) and optimize its catalytic activity and stability, engineering of size and interfacial chemical properties, as well as controllable support are of ultimate importance. Here, the concept of coating uniform thin Co/N‐doped carbon layers into the mesopore surfaces of mesoporous silica is proposed for heterogeneous aqueous catalysis. To approach the target, a one‐step solvent‐free melting‐assisted coating process, i.e., heating a mixture of a cobalt salt, an amino acid (AA), and a mesoporous silica, is developed for the synthesis of mesoporous composites with thin Co/N‐doped carbon layers uniformly coated within mesoporous silica, high surface areas (250–630 m² g⁻¹), ordered mesopores (7.0–8.4 nm), and high water dispersibility. The strong silica/AA adhesive interactions and AA cohesive interactions direct the uniform coating process. The metal/N coordinating, carbon anchoring, and mesopore confining lead to the formation of tiny Co nanoclusters. The carbon intercalation and N coordination optimize the interfacial properties of Co for catalysis. The optimized catalyst exhibits excellent catalytic performance for tandem hydrogenation of nitrobenzene and dehydrogenation of NaBH₄ with well‐matched reaction kinetics, 100% conversion and selectivity, high turnover frequencies, up to ≈6.06 mol_nitrobenzene mol_Co⁻¹ min⁻¹, the highest over transition‐metal catalysts, and excellent stability and magnetic separability.     

Gallium Complexes in Three‐Layer Organic Electroluminescent Devices

Organic light‐emitting diodes fabricated by subsequently spin‐coating two layers—a hole‐transporting followed by a metal chelate emissive layer—onto poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) are presented for the first time. The electron–hole recombination occurs in a layer consisting of Ga complexes (see Figure), which exhibit high fluorescence quantum yields, and their emission spectra are blue‐shifted relative to that of tris(8‐hydroxyquinoline) aluminum. By doping this spin‐coated emission layer with fluorescent emitters the emission band can be shifted within the visible spectral range.     

AFM characterisation of sol‐gel TiO2 films deposited on stainless steel

One‐layer, two‐layer and three‐layer titania films on AISI 304 stainless steel were deposited by sol‐gel process and dip‐coating method. Two sols were prepared by using titanium isopropoxide as a precursor, propanol as a solvent, nitric acid as a catalyst and acetylacetone for peptization. Both of the prepared sols contained the same amount of mentioned components, the only difference was in the addition of polyethylene glycol (PEG) as templating reagent to one of the sols. After calcination at 550°C, deposited films on the stainless steel substrate were characterized by atomic force microscope (AFM). Influence of layer number as well as addition of polyethylene glycol on morphology of titania films was analysed and discussed. Generally, by increasing the number of layers and by addition of polyethylene glycol, roughness parameters increase by changing surface topography. The surface topography analysis is very important when choosing the adequate industrial application of prepared layers.     

Substrate Patterning Using Regular Macroporous Block Copolymer Monoliths as Sacrificial Templates and as Capillary Microstamps

Polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) monoliths containing regular arrays of macropores (diameter ≈1.1 µm, depth ≈0.7 µm) at their surfaces are used to pattern substrates by patterning modes going beyond the functionality of classical solid elastomer stamps. In a first exemplary application, the macroporous PS‐b‐P2VP monoliths are employed as sacrificial templates for the deposition of NaCl nanocrystals and topographically patterned iridium films. One NaCl nanocrystal per macropore is formed by evaporation of NaCl solutions filling the macropores followed by iridium coating. Thermal PS‐b‐P2VP decomposition yields topographically patterned iridium films consisting of ordered arrays of hexagonal cells, each of which contains one NaCl nanocrystal. For the second exemplary application, spongy‐continuous mesopore systems are generated in the macroporous PS‐b‐P2VP monoliths by selective‐swelling induced pore generation. Infiltrating the spongy‐continuous mesopore systems with ink allows capillary microstamping of continuous ink films with holes at the positions of the macropores onto glass slides compatible with advanced light microscopy. Capillary microstamping can be performed multiple times under ambient conditions without reinking and without quality deterioration of the stamped patterns. The macroporous PS‐b‐P2VP monoliths are prepared by double replication of primary macroporous silicon molds via secondary polydimethylsiloxane molds.     

Roll‐to‐Roll Production of Layer‐Controlled Molybdenum Disulfide: A Platform for 2D Semiconductor‐Based Industrial Applications

A facile methodology for the large‐scale production of layer‐controlled MoS₂ layers on an inexpensive substrate involving a simple coating of single source precursor with subsequent roll‐to‐roll‐based thermal decomposition is developed. The resulting 50 cm long MoS₂ layers synthesized on Ni foils possess excellent long‐range uniformity and optimum stoichiometry. Moreover, this methodology is promising because it enables simple control of the number of MoS₂ layers by simply adjusting the concentration of (NH₄)₂MoS₄. Additionally, the capability of the MoS₂ for practical applications in electronic/optoelectronic devices and catalysts for hydrogen evolution reaction is verified. The MoS₂‐based field effect transistors exhibit unipolar n‐channel transistor behavior with electron mobility of 0.6 cm² V^?1 s^?1 and an on‐off ratio of ≈10³. The MoS₂‐based visible‐light photodetectors are fabricated in order to evaluate their photoelectrical properties, obtaining an 100% yield for active devices with significant photocurrents and extracted photoresponsivity of ≈22 mA W^?1. Moreover, the MoS₂ layers on Ni foils exhibit applicable catalytic activity with observed overpotential of ≈165 mV and a Tafel slope of 133 mV dec^?1. Based on these results, it is envisaged that the cost‐effective methodology will trigger actual industrial applications, as well as novel research related to 2D semiconductor‐based multifaceted applications.     

On‐line Quality Control of Coated Glass. On‐line Qualitätskontrolle von beschichtetem Glas

Properties of optical coatings (e.g. low‐e or solar control) can be described and controlled using transmittance, reflectance and sheet resistance measurements. Multiple in situ transmittance measurement points allow a quick response to adjust different coating processes (layer thickness and homogeneity). For the final characterization of the coated substrate ex situ transmittance, reflectance and sheet resistance measurements are used. Accurate and reproducible measurements in a combination with Reverse Engineering methods admit monitoring all layers and in this way detecting slight drifts.