ABSTRACT
We apply Fourier-transform terahertz spectroscopy to investigate the deformation of poly(2-ethylcyanoacrylic) adhesive (PECA) on a polyethylene substrate. The terahertz absorption spectra of the PECA samples were measured over the frequency range 1-10 THz, and absorption peaks from the adhesive layer were identified at 5.70, 6.23, and 7.55-9.12 THz. The PECA samples were then degraded via a hydration reaction, with the terahertz spectra showing a decrease in the intensity of the main peaks of PECA with increasing water degradation time. This study demonstrates the potential of terahertz spectroscopy for the continuous monitoring of the degradation of an adhesive layer.
ABSTRACT
Ultraviolet (UV) nanoimprint lithography is a promising nanofabrication technology with cost efficiency and high throughput for sub-20 nm size semiconductor, data storage, and optical devices. To test formability of organic resist mask patterns, we investigated whether the type of polymerizable di(meth)acrylate monomer affected the fabrication of cured resin nanopillars by UV nanoimprinting using molds with pores of around 20 nm. We used carbon-coated, porous, anodic aluminum oxide (AAO) films prepared by electrochemical oxidation and thermal chemical vapor deposition as molds, because the pore diameter distribution in the range of 10-40 nm was suitable for combinatorial testing to investigate whether UV-curable resins comprising each monomer were filled into the mold recesses in UV nanoimprinting. Although the UV-curable resins, except for a bisphenol A-based one, detached from the molds without pull-out defects after radical photopolymerization under UV light, the number of cured resin nanopillars was independent of the viscosity of the monomer(s) in each resin. The number of resin nanopillars increased and their diameter decreased as the number of hydroxy groups in the aliphatic diacrylate monomers increased. It was concluded that the filling of the carbon-coated pores having diameters of around 20 nm with UV-curable resins was promoted by the presence of hydroxy groups in the aliphatic di(meth)acrylate monomers.
ABSTRACT
We used fluorescence microscopy to show that low adsorption of resin components by a mold surface was necessary for continuous ultraviolet (UV) nanoimprinting, as well as generation of a low release energy on detachment of a cured resin from a template mold. This is because with low mold pollution, fracture on demolding occurred at the interface between the mold and cured resin surfaces rather than at the outermost part of the cured resin. To achieve low mold pollution, we investigated the radical photopolymerization behaviors of fluorescent UV-curable resins and the mechanical properties (fracture toughness, surface hardness, and release energy) of the cured resin films for six types of di(meth)acrylate-based monomers with similar chemical structures, in which polar hydroxy and aromatic bulky bisphenol moieties and methacryloyl or acryloyl reactive groups were present or absent. As a result, we selected bisphenol A glycerolate dimethacrylate (BPAGDM), which contains hydroxy, bisphenol, and methacryloyl moieties, which give good mechanical properties, monomer bulkiness, and mild reactivity, respectively, as a suitable base monomer for UV nanoimprinting under an easily condensable alternative chlorofluorocarbon (HFC-245fa) atmosphere. The fluorescent UV-curable BPAGDM resin was used for UV nanoimprinting and lithographic reactive ion etching of a silicon surface with 32 nm line-and-space patterns without a hard metal layer.
ABSTRACT
Directed self-assembly (DSA) of block copolymers (BCPs), either by selective wetting of surface chemical prepatterns or by graphoepitaxial alignment with surface topography, has ushered in a new era for high-resolution nanopatterning. These pioneering approaches, while effective, require expensive and time-consuming lithographic patterning of each substrate to direct the assembly. To overcome this shortcoming, nanoimprint molds--attainable via low-cost optical lithography--were investigated for their potential to be reusable and efficiently template the assembly of block copolymers (BCPs) while under complete confinement. Nanoimprint directed self-assembly conveniently avoids repetitive and expensive chemical or topographical prepatterning of substrates. To demonstrate this technique for high-resolution nanofabrication, we aligned sub-10 nm resolution nanopatterns using a cylinder-forming, organic-inorganic hybrid block copolymer, polystyrene-block-polydimethylsiloxane (PS-b-PDMS). Nanopatterns derived from oxidized PDMS microdomains were successfully transferred into the underlying substrate using plasma etching. In the development phase of this procedure, we investigated the role of mold treatments and pattern geometries as DSA of BCPs are driven by interfacial chemistry and physics. In the optimized route, silicon molds treated with PDMS surface brushes promoted rapid BCP alignment and reliable mold release while appropriate mold geometries provided a single layer of cylinders and negligible residual layers as required for pattern transfer. Molds thus produced were reusable to the same efficacy between nanoimprints. We also demonstrated that shear flow during the nanoimprint process enhanced the alignment of the BCP near open edges, which may be engineered in future schemes to control the BCP microdomain alignment kinetics during DSA.
ABSTRACT
Heteromolecular layers consisting of quaterrylene (QT) and terrylene-3,4,11,12-tetracarboximide (TTCDI-C12) were prepared on SiO2 surfaces and the electronic energy level alignment at TTCDI-C12/QT interface was examined. TTCDI-C12 layers were grown in nearly perpendicular orientation on QT layers by an ultraslow deposition technique, thereby achieving formation of a well-defined TTCDI-C12/QT interface. Atomic force microscopy (AFM) measurements ensured excellent surface flatness of each layer, surface roughnesses of which were comparable to that of pristine SiO2. Energy level alignment at the heteromolecular interface was evaluated by using ultraviolet photoelectron spectroscopy (UPS) and optical absorption measurements. No shift in energy level was served at the heteromolecular interface, indicating that charge transfer does not occur and a dipole moment is not formed at the well-defined TTCDI-C12/QT interface.
ABSTRACT
We investigated the evolution of quaterrylene thin films on SiO(2) and on an octadecyltrichlorosilane self-assembled monolayer (OTS-SAM) to examine the impact of film strains on the growth processes and evolving structure. Surface modification by SAMs allowed tailoring of the growth process from a Stranski-Krastanov (SK) mode (layer-plus-island) on the SiO(2) surface to a Frank-van der Merwe mode (layer-by-layer) on the OTS surface. Detailed structural analysis by x-ray diffraction techniques confirmed that the SK mode was driven by lattice strain in the initial wetting layers on the SiO(2) surface. On the other hand, strain-free wetting layers were already formed at the beginning of growth on the OTS surface, thereby suppressing three-dimensional island formation. Moreover, the films on the SiO(2) surface were found to incorporate high microstrain induced by crystal defects such as dislocations and a mosaic structure. In contrast, few crystal defects were present in the films on OTS surface, demonstrating that OTS treatment enables marked improvement of the molecular alignment. These results clearly indicate that the lattice strain induced by the molecular-substrate interaction is essential for controlling the overall growth process.
