Multilayer fabrication of unobtrusive poly(dimethylsiloxane) nanobrush for tunable cell adhesion.

Precise modulation of polymer brush in its thickness and grafting density can cause unexpected cell behaviors and regulated bioactivities. Herein, a nanoscale poly(dimethylsiloxane) (PDMS) brush was employed to use as a controllable material for cell adhesion. Facile fabrication of ultrathin monolayer PDMS nanobrush on an underlying substrate facilitated regaining cell adhesion through long-range cell attractive forces such as the van der Waals forces. We showed that cell adhesion is diminished by increasing the number of nanobrush layers, causing a gradual decrease of the effectiveness of the long-range force. The result demonstrates that ultrathin PDMS nanobrush can either promote or inhibit cell adhesion, which is required for various biomedical fields such as tissue-engineering, anti-fouling coating, and implantable biomaterials and sensors.

Photoactive Poly(3-hexylthiophene) Nanoweb for Optoelectrical Stimulation to Enhance Neurogenesis of Human Stem Cells.

Optoelectrical manipulation has recently gained attention for cellular engineering; however, few material platforms can be used to efficiently regulate stem cell behaviors via optoelectrical stimulation. In this study, we developed nanoweb substrates composed of photoactive polymer poly(3-hexylthiophene) (P3HT) to enhance the neurogenesis of human fetal neural stem cells (hfNSCs) through photo-induced electrical stimulation. METHODS: The photoactive nanoweb substrates were fabricated by self-assembled one-dimensional (1D) P3HT nanostructures (nanofibrils and nanorods). The hfNSCs cultured on the P3HT nanoweb substrates were optically stimulated with a green light (539 nm) and then differentiation of hfNSCs on the substrates with light stimulation was examined. The utility of the nanoweb substrates for optogenetic application was tested with photo-responsive hfNSCs engineered by polymer nanoparticle-mediated transfection of an engineered chimeric opsin variant (C1V1)-encoding gene. RESULTS: The nanoweb substrates provided not only topographical stimulation for activating focal adhesion signaling of hfNSCs, but also generated optoelectrical stimulation via photochemical and charge-transfer reactions upon exposure to 539 nm wavelength light, leading to significantly enhanced neuronal differentiation of hfNSCs. The optoelectrically stimulated hfNSCs exhibited mature neuronal phenotypes with highly extended neurite formation and functional neuron-like electrophysiological features of sodium currents and action potentials. Optoelectrical stimulation with 539 nm light simultaneously activated both C1V1-modified hfNSCs and nanoweb substrates, which upregulated the expression and activation of voltage-gated ion channels in hfNSCs and further increased the effect of photoactive substrates on neuronal differentiation of hfNSCs. CONCLUSION: The photoactive nanoweb substrates developed in this study may serve as platforms for producing stem cell therapeutics with enhanced neurogenesis and neuromodulation via optoelectrical control of stem cells.

Tracheal reconstruction with a free vascularized myofascial flap: preclinical investigation in a porcine model to human clinical application.

Although there are various methods for tracheal reconstruction, such as a simple approximation with suturing and coverage with adjacent soft tissue or muscle, large defects >50% of the tracheal length still present a clinical challenge. Tissue engineering, a recent promising way to possibly resolve this problem, requires a long preparatory period for stem cell seeding on a scaffold and relatively invasive procedures for stem cell harvesting. As an alternative, we used a vascularized myofascial flap for tracheal reconstruction. In four porcine models, the deep inferior epigastric perforator (DIEP) was used in two and the superior epigastric artery perforator (SEAP) in two. Transformation of the surface of the transplanted myofascial flap was analyzed in the airway environment. The flaps failed in the DIEP group due to venous congestion. At 12 weeks postoperatively, none of SEAP group showed any signs of respiratory distress; the inner surface of the implant exhibited stratified squamous epithelium with sparse cilia. In the clinical setting, a patient who underwent a tracheal reconstruction with a vascularized myofascial flap and 2-year follow-up was in good health with no respiratory distress symptoms.

Deformable Electronics: Conducting Polymer Dough for Deformable Electronics (Adv. Mater. 22/2016).

A simple strategy for changing a brittle conducting polymer ( PEDOT: PSS) into a solution-processed highly deformable viscoelastic polymer is presented by H.-K. Baik, U. Jeong, and co-workers on page 4455. The storage modulus versus loss modulus of the polymer is adjusted to control the viscoelastic properties to fit the properties required in deformable electronics. Rapid self-healing of conductivity, custom-designed LEDs with complex micropatterns, and foldable stretchable LEDs are demonstrated.

Adopting Novel Strategies in Achieving High-Performance Single-Layer Network Structured ZnO Nanorods Thin Film Transistors.

High-performance, solution-processed transparent and flexible zinc oxide (ZnO) nanorods (NRs)-based single layer network structured thin film transistors (TFTs) were developed on polyethylene terephthalate (PET) substrate at 100 °C. Keeping the process-temperature under 100 °C, we have improved the device performance by introducing three low temperature-based techniques; regrowing ZnO to fill the void spaces in a single layer network of ZnO NRs, passivating the back channel with polymer, and adopting ZrO2 as the high-k dielectric. Notably, high-k amorphous ZrO2 was synthesized and deposited using a novel method at an unprecedented temperature of 100 °C. Using these methods, the TFTs exhibited a high mobility of 1.77 cm(2)/V·s. An insignificant reduction of 2.18% in mobility value after 3000 cycles of dynamic bending at a radius of curvature of 20 mm indicated the robust mechanical nature of the flexible ZnO NRs SLNS TFTs.

Microscale Soft Patterning for Solution Processable Metal Oxide Thin Film Transistors.

We introduce a microscale soft pattering (MSP) route utilizing contact printing of chemically inert sub-nanometer thick low molecular weight (LMW) poly(dimethylsiloxane) (PDMS) layers. These PDMS layers serve as a release agent layer between the n-type Ohmic metal and metal oxide semiconductors (MOSs) and provide a layer that protects the MOS from water in the surrounding environment. The feasibility of our MSP route was experimentally demonstrated by fabricating solution processable In2O3, IZO, and IGZO TFTs with aluminum (Al), a typical n-type Ohmic metal. We have demonstrated patterning gaps as small as 13 µm. The TFTs fabricated using MSP showed higher field-effect-mobility and lower hysteresis in comparison with those made using conventional photolithography.

Conducting Polymer Dough for Deformable Electronics.

UNLABELLED: A simple strategy for changing a brittle conducting polymer ( PEDOT: PSS) into a solution-processed highly deformable viscoelastic polymer is presented. Rapid self-healing of conductivity, customer-designed LEDs with complex micro-patterns, and foldable stretchable LEDs are demonstrated.

Low-temperature, solution-processed ZrO2:B thin film: a bifunctional inorganic/organic interfacial glue for flexible thin-film transistors.

A solution-processed boron-doped peroxo-zirconium oxide (ZrO2:B) thin film has been found to have multifunctional characteristics, providing both hydrophobic surface modification and a chemical glue layer. Specifically, a ZrO2:B thin film deposited on a hydrophobic layer becomes superhydrophilic following ultraviolet-ozone (UVO) treatment, whereas the same treatment has no effect on the hydrophobicity of the hydrophobic layer alone. Investigation of the ZrO2:B/hydrophobic interface layer using angle-resolved X-ray photoelectron spectroscopy (AR XPS) confirmed it to be chemically bonded like glue. Using the multifunctional nature of the ZrO2:B thin film, flexible amorphous indium oxide (In2O3) thin-film transistors (TFTs) were subsequently fabricated on a polyimide substrate along with a ZrO2:B/poly-4-vinylphenol (PVP) dielectric. An aqueous In2O3 solution was successfully coated onto the ZrO2:B/PVP dielectric, and the surface and chemical properties of the PVP and ZrO2:B thin films were analyzed by contact angle measurement, atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The surface-engineered PVP dielectric was found to have a lower leakage current density (Jleak) of 4.38 × 10(-8) A/cm(2) at 1 MV/cm, with no breakdown behavior observed up to a bending radius of 5 mm. In contrast, the electrical characteristics of the flexible amorphous In2O3 TFT such as on/off current ratio (Ion/off) and electron mobility remained similar up to 10 mm of bending without degradation, with the device being nonactivated at a bending radius of 5 mm. These results suggest that ZrO2:B thin films could be used for low-temperature, solution-processed surface-modified flexible devices.

Strong hydrophobizer: laterally chemisorbed low-molecular-weight polydimethylsiloxane.

We introduce a siloxane chain-based hydrophobizer that exhibits superior thermal and chemical stability compared to the conventional hydrophobizing silane agent under conditions of over 300 °C and pH 2-13. To demonstrate the capability of the siloxane chain-based hydrophobizer to serve as a highly robust chemical surface modifier, we present two applications: the formation of fine metal nanoparticles with a narrow size distribution by thermal aggregation of a metal thin film and the selective deposition of a ruthenium thin film by atomic layer deposition.

Polythiophene nanofibril bundles surface-embedded in elastomer: a route to a highly stretchable active channel layer.

A stretchable polymer channel layer for organic field-effect transistors is obtained by spin-coating a blend solution of polythiophene and rubber polymer. A network of the polythiophene nanofibril bundles surface-embedded in the rubber matrix allows large stretchability of the polythiophene film layer.

Efficient hydrogen evolution by mechanically strained MoS2 nanosheets.

We demonstrated correlations between mechanically bent tensile-strain-induced two-dimensional MoS2 nanosheets (NSs) and their electrochemical activities toward the hydrogen evolution reaction (HER). The tensile-strain-induced MoS2 NSs showed significantly steeper polarization curves and lower Tafel slopes than the strain-free ones, which is consistent with the simple d-band model. Furthermore, the mechanical strain increased the electrochemical activities of all the NSs toward the HER except those loaded with high MoS2 mass. Mechanically bending MoS2 NSs to induce tensile strain enables the production of powerful, efficient electrocatalysis systems for evolving hydrogen.

Effect of PEDOT Nanofibril Networks on the Conductivity, Flexibility, and Coatability of PEDOT:PSS Films.

The use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in electrodes and electrical circuits presents a number of challenges that are yet to be overcome, foremost amongst which are its relatively low conductivity, low coatability on hydrophobic substrates, and decreased conductivity at large strains. With this in mind, this study suggests a simple way to simultaneously address all of these issues through the addition of a small amount of a nonionic surfactant (Triton X-100) to commercial PEDOT:PSS solutions. This surfactant is shown to considerably reduce the surface tension of the PEDOT:PSS solution, thus permitting conformal coatings of PEDOT:PSS thin film on a diverse range of hydrophobic substrates. Furthermore, this surfactant induces the formation of PEDOT nanofibrils during coating, which led to the high conductivity values and mechanical stability at large strains (ε=10.3%). Taking advantage of the superior characteristics of these PEDOT:PSS thin films, a highly flexible polymer solar cell was fabricated. The power conversion efficiency of this solar cell (3.14% at zero strain) was preserved at large strains (ε=7.0%).

Enhanced air stability of polymer solar cells with a nanofibril-based photoactive layer.

In spite of the rapid increase in the power conversion efficiency (PCE) of polymer solar cells (PSCs), the poor stability of the photoactive layer in air under sunlight is a critical problem blocking commercialization of PSCs. This study investigates the photo-oxidation behavior of a bulk-heterojunction (BHJ) photoactive film made of single-crystalline poly(3-hexlythiophene) (P3HT) nanofibrils and fullerene derivatives [phenyl-C61-butyric methyl ester (PCBM), indene-C 60 bisadduct (ICBA)]. Because the single-crystalline P3HT nanofibrils had tightly packed π-π stacking, the permeation of oxygen and water into the nanofibrils was significantly reduced. Chemical changes in P3HT were not apparent in the nanofibrils, and hence the air stability of the nanofibril-based BHJ film was considerably enhanced as compared with conventional BHJ films. The chemical changes were monitored by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, and UV-vis absorbance. Inverted PSCs made of the nanofibril-based BHJ layer also showed significantly enhanced air stability under sunlight. The nanofibril-based solar cell maintained more than 80% of its initial PCE after 30 days of continuous exposure to sunlight (AM 1.5G, 100 mW/cm(2)), whereas the PCE of the conventional BHJ solar cell decreased to 20% of its initial PCE under the same experimental conditions.

A low temperature Co-fired ceramic-based dielectrophoretic device for manipulating micro and nanostructure materials.

A dielectophoretic (DEP) device fabricated by a conventional low temperature co-fired ceramic (LTCC) process, for manipulating micro and nanostructure materials, such as spherical polystyrene microspheres, titanium dioxide (TiO2) nanotubes, and silver (Ag) nanowires, is described. To generate a non-uniform electric field, a castellated electrode configuration was applied to the LTCC-based DEP device using a screen printing method. The actual motions of the micro and nanostructure materials under both a positive and a negative DEP force were observed in detail and the findings compared with numerical simulation data for the electric field distribution. The performance of the LTCC-based DEP device for separating and trapping was evaluated and potential applications are discussed.

Boron-doped peroxo-zirconium oxide dielectric for high-performance, low-temperature, solution-processed indium oxide thin-film transistor.

We developed a solution-processed indium oxide (In2O3) thin-film transistor (TFT) with a boron-doped peroxo-zirconium (ZrO2:B) dielectric on silicon as well as polyimide substrate at 200 °C, using water as the solvent for the In2O3 precursor. The formation of In2O3 and ZrO2:B films were intensively studied by thermogravimetric differential thermal analysis (TG-DTA), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT IR), high-resolution X-ray diffraction (HR-XRD), and X-ray photoelectron spectroscopy (XPS). Boron was selected as a dopant to make a denser ZrO2 film. The ZrO2:B film effectively blocked the leakage current at 200 °C with high breakdown strength. To evaluate the ZrO2:B film as a gate dielectric, we fabricated In2O3 TFTs on the ZrO2:B dielectrics with silicon substrates and annealed the resulting samples at 200 and 250 °C. The resulting mobilities were 1.25 and 39.3 cm(2)/(V s), respectively. Finally, we realized a flexible In2O3 TFT with the ZrO2:B dielectric on a polyimide substrate at 200 °C, and it successfully operated a switching device with a mobility of 4.01 cm(2)/(V s). Our results suggest that aqueous solution-processed In2O3 TFTs on ZrO2:B dielectrics could potentially be used for low-cost, low-temperature, and high-performance flexible devices.

Effects of solution temperature on solution-processed high-performance metal oxide thin-film transistors.

Herein, we report a novel and easy strategy for fabricating solution-processed metal oxide thin-film transistors by controlling the dielectric constant of H2O through manipulation of the metal precursor solution temperature. As a result, indium zinc oxide (IZO) thin-film transistors (TFTs) fabricated from IZO solution at 4 °C can be operated after annealing at low temperatures (∼250 °C). In contrast, IZO TFTs fabricated from IZO solutions at 25 and 60 °C must be annealed at 275 and 300 °C, respectively. We also found that IZO TFTs fabricated from the IZO precursor solution at 4 °C had the highest mobility of 12.65 cm2/(V s), whereas the IZO TFTs fabricated from IZO precursor solutions at 25 and 60 °C had field-effect mobility of 5.39 and 4.51 cm2/(V s), respectively, after annealing at 350 °C. When the IZO precursor solution is at 4 °C, metal cations such as indium (In3+) and zinc ions (Zn2+) can be fully surrounded by H2O molecules, because of the higher dielectric constant of H2O at lower temperatures. These chemical complexes in the IZO precursor solution at 4 °C are advantageous for thermal hydrolysis and condensation reactions yielding a metal oxide lattice, because of their high potential energies. The IZO TFTs fabricated from the IZO precursor solution at 4 °C had the highest mobility because of the formation of many metal-oxygen-metal (M-O-M) bonds under these conditions. In these bonds, the ns-orbitals of the metal cations overlap each other and form electron conduction pathways. Thus, the formation of a high proportion of M-O-M bonds in the IZO thin films is advantageous for electron conduction, because oxide lattices allow electrons to travel easily through the IZO.

Fabrication of a multidomain and ultrafast-switching liquid crystal alignment layer using contact printing with a poly(dimethylsiloxane) stamp.

A compartmentalized multidomain alignment state of a layer of liquid crystal display is achieved using an ultrathin, highly transparent, and ultrafast-responsive alignment layer fabricated by a simple method. The ultrathin alignment layer consists of a self-assembled oligomer layer of poly(dimethylsiloxane) (PDMS) formed by utilizing the oligomers that diffuse out from a PDMS elastomer stamp during a contact printing process.

Low-temperature, high-performance solution-processed thin-film transistors with peroxo-zirconium oxide dielectric.

We demonstrated solution-processed thin film transistors on a peroxo-zirconium oxide (ZrO(2)) dielectric with a maximum temperature of 350 °C. The formation of ZrO(2) films was investigated by TG-DTA, FT-IR, and XPS analyses at various temperatures. We synthesized a zirconium oxide solution by adding hydrogen peroxide (H(2)O(2)). The H(2)O(2) forms peroxo groups in the ZrO(2) film producing a dense-amorphous phase and a smooth surface film. Because of these characteristics, the ZrO(2) film successfully blocked leakage current even in annealing at 300 °C. Finally, to demonstrate that the ZrO(2) film is dielectric, we fabricated thin-film transistors (TFTs) with a solution-processed channel layer of indium zinc oxide (IZO) on ZrO(2) films at 350 °C. These TFTs had a mobility of 7.21 cm(2)/(V s), a threshold voltage (V(th)) of 3.22 V, and a V(th) shift of 1.6 V under positive gate bias stress.

Playing with dimensions: rational design for heteroepitaxial p-n junctions.

A design for a heteroepitaxial junction by the way of one-dimensional wurzite on a two-dimensional spinel structure in a low-temperature solution process was introduced, and it's capability was confirmed by successful fabrication of a diode consisting of p-type cobalt oxide (Co(3)O(4)) nanoplate/n-type zinc oxide (ZnO) nanorods, showing reasonable electrical performance. During thermal decomposition, the 30° rotated lattice orientation of Co(3)O(4) nanoplates from the orientation of ß-Co(OH)(2) nanoplates was directly observed using high-resolution transmission electron microscopy. The epitaxial relations and the surface stress-induced ZnO nanowire growth on Co(3)O(4) were well supported using the first-principles calculations. Over the large area, (0001) preferred oriented ZnO nanorods epitaxially grown on the (111) plane of Co(3)O(4) nanoplates were experimentally obtained. Using this epitaxial p-n junction, a diode was fabricated. The ideality factor, turn-on voltage, and rectifying ratio of the diode were measured to be 2.38, 2.5 V and 10(4), respectively.