Fabrication of extreme ultraviolet lithography pellicle with nanometer-thick graphite film by sublimation of camphor supporting layer.

An extreme ultraviolet (EUV) pellicle consists of freestanding thin films on a frame; these films are tens of nanometers in thickness and can include Si, SiNX, or graphite. Nanometer-thick graphite films (NGFs), synthesized via chemical vapor deposition on a metal catalyst, are used as a pellicle material. The most common method to transfer NGFs onto a substrate or a frame is to use polymethyl methacrylate (PMMA) as a supporting layer. However, this PMMA-mediated technique involves several disadvantages in term of manufacturing NGF EUV pellicles. When removing the PMMA using acetone or O2plasma, defects or deflections can occur in the NGFs. Furthermore, PMMA residues are generally present on large-area NGFs. In this study, a transfer method using camphor instead of PMMA as the supporting layer was developed to overcome these problems. After the camphor/NGF was formed on the frame, camphor was removed via sublimation in an atmosphere of ethanol vapor. This study investigated the deposition and sublimation of camphor, and confirmed that no residue was present and no deflection or defects were observed in the NGFs. Thus, a large-area NGF pellicle was successfully fabricated using the camphor transfer process.

A flexible insulator of a hollow SiO2 sphere and polyimide hybrid for flexible OLEDs.

The fabrication of interlayer dielectrics (ILDs) in flexible organic light-emitting diodes (OLEDs) not only requires flexible materials with a low dielectric constant, but also ones that possess the electrical, thermal, chemical, and mechanical properties required for optimal device performance. Porous polymer-silica hybrid materials were prepared to satisfy these requirements. Hollow SiO2 spheres were synthesized using atomic layer deposition (ALD) and a thermal calcination process. The hybrid film, which consists of hollow SiO2 spheres and polyimide, shows a low dielectric constant of 1.98 and excellent thermal stability up to 500 °C. After the bending test for 50 000 cycles, the porous hybrid film exhibits no degradation in its dielectric constant or leakage current. These results indicate that the hybrid film made up of hollow SiO2 spheres and polyimide (PI) is useful as a flexible insulator with a low dielectric constant and high thermal stability for flexible OLEDs.

High performance CNT point emitter with graphene interfacial layer.

Carbon nanotubes (CNTs) have great potential in the development of high-power electron beam sources. However, for such a high-performance electronic device, the electric and thermal contact problem between the metal and CNTs must be improved. Here, we report graphene as an interfacial layer between the metal and CNTs to improve the interfacial contact. The interfacial graphene layer results in a dramatic decrease of the electrical contact resistance by an order of 2 and an increase of the interfacial thermal conductivity by 16%. Such a high improvement in the electrical and thermal interface leads to superior field emission performance with a very low turn-on field of 1.49 V µm(-1) at 10 µA cm(-2) and a threshold field of 2.00 V µm(-1) at 10 mA cm(-2), as well as the maximum current of 16 mA (current density of 2300 A cm(-2)).

Nanocrystalline-graphene-tailored hexagonal boron nitride thin films.

Unintentionally formed nanocrystalline graphene (nc-G) can act as a useful seed for the large-area synthesis of a hexagonal boron nitride (h-BN) thin film with an atomically flat surface that is comparable to that of exfoliated single-crystal h-BN. A wafer-scale dielectric h-BN thin film was successfully synthesized on a bare sapphire substrate by assistance of nc-G, which prevented structural deformations in a chemical vapor deposition process. The growth mechanism of this nc-G-tailored h-BN thin film was systematically analyzed. This approach provides a novel method for preparing high-quality two-dimensional materials on a large surface.

Filtration-wet transferred transparent conducting films of mm long carbon nanotubes grown using water-assisted chemical vapor deposition.

Transparent conducting films (TCF) made up from carbon nanotubes (CNTs) have a tremendous potential in replacing the indium tin oxide films. Compare to single wall CNTs multiwall CNTs are more metallic and are more suitable candidate for the TCF. In this letter we report the use of selectively grown mm-scale, few-wall, vertically aligned CNTs for the fabrication of TCF. Water-assisted chemical vapor deposition was used to grow the mm-scale CNTs within short growth time. A special post-growth water-vapor treatment allowed us to remove the catalyst-free CNT forest very easily from the substrate and use it for the further process. A filtration-wet transfer process was used to form the TCF. The TCF shows sheet resistance of 228 omega/sq. at 72% transparency (at 550 nm). The ratio of optical conductivity to dc conductivity was observed in between 0.21 to 0.25 for below 80% transmission.

Field emission properties of a graphene/polymer composite.

Thin graphene/polymer sheet composites were fabricated using easily soluble expanded graphite (ESEG), and their field emission (FE) parameters were examined. Due to the high dispersability of ESEG, a stable graphene suspension was prepared by ultrasonication in toluene without the need for a surfactant. The suspension consisted of exfoliated graphene sheets with a thickness of 1 - 2 nm. Using a calendering process, the solution was further shear mixed with ethyl cellulose to obtain a well-dispersed graphene/polymer composite. The composite was screen printed onto a conducing substrate to fabricate the FE cathode layers. The FE measurements were taken in a diode configuration at an applied electrostatic field and inter-electrode distance of 1.7 to 6 V/microm and approximately 200 microm, respectively. The threshold turn-on-field was approximately 3.5 V/microm at a current density of approximately 10 microA/cm2 with a corresponding mean field enhancement factor of 1350 +/- 50. Emission occurred mainly from the edges and bends of the graphene layers. The luminescence uniformity of the composite cathode layers was examined using a phosphor-coated anode.

Solution-processed, high-performance n-channel organic microwire transistors.

The development of solution-processable, high-performance n-channel organic semiconductors is crucial to realizing low-cost, all-organic complementary circuits. Single-crystalline organic semiconductor nano/microwires (NWs/MWs) have great potential as active materials in solution-formed high-performance transistors. However, the technology to integrate these elements into functional networks with controlled alignment and density lags far behind their inorganic counterparts. Here, we report a solution-processing approach to achieve high-performance air-stable n-channel organic transistors (the field-effect mobility (mu) up to 0.24 cm(2)/Vs for MW networks) comprising high mobility, solution-synthesized single-crystalline organic semiconducting MWs (mu as high as 1.4 cm(2)/Vs for individual MWs) and a filtration-and-transfer (FAT) alignment method. The FAT method enables facile control over both alignment and density of MWs. Our approach presents a route toward solution-processed, high-performance organic transistors and could be used for directed assembly of various functional organic and inorganic NWs/MWs.

Fabrication of a 100 × 100 mm2 nanometer-thick graphite pellicle for extreme ultraviolet lithography by a peel-off and camphor-supported transfer approach.

An extreme ultraviolet (EUV) lithography pellicle is used to physically protect a mask from contaminants during the EUV exposure process and needs to have a high EUV transmittance. The EUV pellicle should be fabricated using a freestanding thin film with several tens of nanometer thickness in an area of 110 × 142 mm2, which is a challenging task. Here, we propose a peel-off approach to directly detach the nanometer-thick graphite film (NGF)/Ni film from SiO2/Si wafer and significantly shorten the etching time of the Ni film. Combined with the residue-damage-free transfer method that used camphor as a supporting layer, we successfully fabricated a large-area (100 × 100 mm2) NGF pellicle with a thickness of ∼20 nm, and an EUV transmittance of ∼87.2%.

Growth of carbon nanotube field emitters on single strand carbon fiber: a linear electron source.

The multi-stage effect has been revisited through growing carbon nanotube field emitters on single strand carbon fiber with a thickness of 11 µm. A prepared linear electron source exhibits a turn-on field as low as 0.4 V µm(-1) and an extremely high field enhancement factor of 19,300, when compared with those results from reference nanotube emitters grown on flat silicone wafer; 3.0 V µm(-1) and 2500, respectively. In addition, we introduce a novel method to grow nanotubes uniformly around the circumference of carbon fibers by using direct resistive heating on the continuously feeding carbon threads. These results open up not only a new path for synthesizing nanocomposites, but also offer an excellent linear electron source for special applications such as backlight units for liquid crystal displays and multi-array x-ray sources.

Hard Coating Materials Based on Photo-Reactive Silsesquioxane for Flexible Application: Improvement of Flexible and Hardness Properties by High Molecular Weight.

EPOSS of polyhedral oligomeric silsesquioxanes (POSS) mixture structure and LPSQ of ladder-like polysilsesquioxane (LPSQ) structure were synthesized via sol-gel reaction. EPSQ had a high molecular weight due to polycondensation by potassium carbonate. The EPSQ film showed uniform surface morphology due to regular double-stranded structure. In contrast, the EPOSS-coated film showed nonuniform surface morphology due to strong aggregation. Due to the aggregation, the EPOSS film had shorter d-spacing (d1) than the EPSQ film in XRD analysis. In pencil hardness and nanoindentation analysis, EPSQ film showed higher hardness than the EPOSS film due to regular double-stranded structure. In addition, in the in-folding (r = 0.5 mm) and out-folding (r = 5 mm) tests, the EPSQ film did not crack unlike the EPOSS coated film.

Drug release behavior from nanoporous anodic aluminum oxide.

In this study, we developed a new drug delivery system using anodic oxidation. The growth of a porous oxide layer on aluminum under anodic bias in various electrolytes has been studied for more than 40 years. Anodic Aluminum Oxide (AAO) has many uniform nanopores on its surface. This nanoporous surface can be used for drug storage. The effects of the diameter and depth of the AAO on the release characteristics of a drug were investigated. Paclitaxel was used for the drug loading and release test. Paclitaxel was loaded on the inside of the AAO by ultrasonication. The amount of the drug released from the AAO was analyzed by high performance liquid chromatography (HPLC). The pore size did not affect the drug release behavior. However, the depth of the pores had a significant influence on the release rate of the drug.

Three-dimensional CuO nanobundles consisted of nanorods: hydrothermal synthesis, characterization, and formation mechanism.

Novel monoclinic CuO nanobundles, 0.8-1 microm in size, were synthesized at 130 degrees C in the presence of sodium dodecyl benzenesulfonate (SDBS) by a simple hydrothermal method. Each nanobundle was comprised of many nanorods with one ends growing together to form a center and another ends radiating laterally from this center. The length and the diameter of these assembled nanorods are in the range of 200-300 nm and about 20-30 nm, respectively. HRTEM and SAED results indicated that the CuO nanorods grow along the [010] direction. An investigation of the hydrothermal process revealed that the reaction time, temperature and surfactant play important roles in the formation of the resultant CuO nanostructures. Isolated CuO nanorods were obtained when the temperature was increased to 190 degrees C, and CuO microflowers composed of many nanosheets were produced at 130 degrees C when cetyltrimethylammonium bromide (CTAB) was employed instead of SDBS. The possible mechanism for the formation of these CuO nanostructures was discussed simply on the basis of the experimental results.

Metallic copper nanostructures synthesized by a facile hydrothermal method.

A facile hydrothermal route has been developed for the synthesis of nearly spherical copper nanoparticles, copper nanocubes and ribbon-like network nanostructures. The as-prepared copper nanostructures were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and UV-vis spectrum analysis. These copper products were fabricated in the presence of surfactant sodium dodecyl benzenesulfonate (SDBS) acting not only as stabilizer but also as size and shape controller via hydrothermal reduction process. HRTEM revealed that the surface of the copper nanostructures was packed with a thin layer of impurities such as oxide combined surfactant or amorphous surfactant. The influence of surfactant concentration and temperature on the resultant copper nanostructures was investigated in details. UV-vis spectra indicated that strong red shift existed for the copper ribbon-like network nanostructures due to the novel morphology as well as the presence of impurities on the surface.

Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process.

Large area of self-organized, free standing anodic titanium oxide (ATO) nanotube membranes with clean surfaces were facilely prepared to desired lengths via electrochemical anodization of highly pure Ti sheets in an ethylene glycol electrolyte, with a small amount of NH4F and H2O at 50 V, followed by self-detachment of the ATO membrane from the Ti substrate using recycling processes. In the first anodization step, the nanowire oxide layer existed over the well-arranged ATO nanotube. After sufficiently rinsing with water, the whole ATO layer was removed from the Ti sheet by high pressure N2 gas, and a well-patterned dimple layer with a thickness of about 30 nm existed on the Ti substrate. By using these naturally formed nano-scale pits as templates, in the second and third anodization process, highly ordered, vertically aligned, and free standing ATO membranes with the anodic aluminum oxide (AAO)-like clean surface were obtained. The inter-pore distance and diameter was 154 +/- 2 nm and 91+/- 2 nm, the tube arrays lengths for 25 and 46 hours were 44 and 70 microm, respectively. The present study demonstrates a simple approach to producing high quality, length controllable, large area TiO2 membrane.

Relationship between surface hydrophobicity and flux for membrane separation.

Surface hydrophobicity of anodic aluminum oxide (AAO) membranes was controlled via carbon coating using the CVD method or O2 plasma treatment with insignificant changes of pore diameter. This study first demonstrated that a larger hydrophobic pore surface and hydrophilic membrane surface are favorable for developing high performance membranes.

One-step exfoliation synthesis of easily soluble graphite and transparent conducting graphene sheets.

Easily soluble expanded graphite is synthesized in a one-step exfoliation process that can be used for the lowcost mass production of graphene for various applications because of the simplicity and speed of the process. The graphene obtained is sufficiently expanded to be dispersed in aqueous solutions with an ordinary surfactant and in organic solvents.

A role of HNO3 on transparent conducting film with single-walled carbon nanotubes.

There is some controversy regarding the effects of HNO3 on films of single-walled carbon nanotubes (SWCNTs). In this study we examined the change in sheet resistance of an HNO3-modified SWCNT film after different drying times at 85 degrees C using various analytical techniques. The shift and suppression in the Raman spectra, bleaching of the transition peaks related to van Hove singularities and a shift in the original peak in the C 1s XPS spectra provided evidence for p-type doping. A decrease in sheet resistance was also observed in the SWCNTs films due to the removal of residual N-methylpyrrolidone solvent on the surface and bundle of SWCNTs. These results suggest that p-type doping has a larger effect on the sheet resistance than the removal of residual N-methylpyrrolidone by an HNO3 treatment.

Patterned carbon nanotube growth using an electron beam sensitive direct writable catalyst.

This paper reports the use of spin coatable Fe naphthenate (Fe(C(11)H(7)O(2))(2)) as an electron beam sensitive direct writable catalyst suitable for growing high quality carbon nanotubes (CNTs). Vertically aligned, densely packed, equal in height, three- to four-walled and 5-7 nm inner diameter CNTs were grown on the nanoscale stripe patterns by water-assisted chemical vapor deposition. The correlation between electron beam dosage and the growth characteristics of CNTs is also discussed.

Fabrication of flexible transparent conductive film (TCF) using single walled carbon nanotubes.

In this work, using single walled carbon nanotubes (SWNTs) made by chemical vapor deposition (CVD) process, transparent conductive film (TCF) was prepared for mass production. The optimum dispersion condition and two step sprays coating of aqueous SWNTs solution and organic polymer solutions have enabled us to achieve the high conductivity, excellent flexibility, and strong adhesion. Through the analysis of particle size and zeta potential of dispersed SWNTs in water, it was found that the particle size and solution stability were reduced as dispersing time increased. Acid treatment of sprayed SWNTs layer removed the surfactant and provided a hole doping effect to SWNTs, resulting in significant reduction of the surface resistance of SWNTs film. Consequently, CVD SWNTs flexible transparent conductive film (surface resistance of 270 ohm/sq, transmittance of 82.3% at 550 nm with substrate effect, and of 93.5% without substrate effect) was developed.

Expanded graphene oxide fibers with high strength and increased elongation.

We report the role of chemically expanded graphite in the fabrication of high-performance graphene oxide fibers by wet spinning. X-ray diffraction peak showed that the interplanar distance of the expanded graphene oxide (EGO) fiber was more than that of graphene oxide (GO) fiber due to the expanded graphite. X-ray photon spectroscopy analysis revealed that EGO was more oxidized than GO. The hydrogen bonding network and secondary intermolecular interaction made the EGO aqueous solution more stable and crystalline, and it was able to be stretched in the coagulation bath. Morphological analysis showed the excellent alignment and compactness of EGO sheets in the fibers. The increased interplanar distance between the EGO sheets favored the edge-to-edge interaction more than the basal plane interaction within the fiber, thus resulting in high mechanical strength (492 MPa) and increased elongation (6.1%).