Photoluminescence variations in organic fluorescent crystals by changing the surface energy of the substrate.

Organic fluorescent crystals were obtained using single-benzene-based diethyl 2,5-dihydroxyterephthalate (DDT) molecules through crystallization from a droplet of the DDT solution on an Au substrate. To control the size of the DDT crystals, the surface energy of the Au substrate was modified with air plasma treatment, producing a hydrophilic surface and a hydrophobic self-assembled monolayer (SAM) coating. The size of DDT crystals increased as the surface energy of the substrate decreased. The averaged cross-section area of the DDT crystals on the Au substrates increased in the order of the air-plasma-treated substrate (∼23.43 µm2) < pristine substrate (∼225.6 µm2) < hydrophobic SAM-coated substrate (∼2240 µm2). On the other hand, the main emission of the DDT crystals redshifted from blue to green as the crystal size increased, which is related to the aggregation of the DDT crystals. Moreover, the coffee-ring effect during the DDT crystallization was hindered by controlling the solvent evaporation conditions. As examples of the application of the proposed technique, patterned DDT crystals were obtained using selectively patterned hydrophobic and hydrophilic substrates.

Tip-based Lithography with a Sacrificial Layer.

The fabrication of a highly controlled gold (Au) nanohole (NH) array via tip-based lithography is improved by incorporating a sacrificial layer-a tip-crash buffer layer. This inclusion mitigates scratches during the nano-indentation process by employing a 300 nm thick poly(methyl methacrylate) layer as a sacrificial layer on top of the Au film. Such a precaution ensures minimal scratches on the Au film, facilitating the creation of sub-50 nm Au NHs with a 15 nm gap between the Au NHs. The precision of this method exceeds that of fabricating Au NHs without a sacrificial layer. Demonstrating its versatility, this Au NH array is utilized in two distinct applications: as a dry etching mask to form a molybdenum disulfide hole array and as a catalyst in metal-assisted chemical etching, resulting in conical-shaped silicon nanostructures. Additionally, a significant electric field is generated when Au nanoparticles (NPs) are placed within the Au NHs. This effect arises from coupling electromagnetic waves, concentrated by the Au NHs and amplified by the Au NPs. A notable result of this configuration is the enhancement factor of surface-enhanced Raman scattering, which is an order of magnitude greater than that observed with just Au NHs and Au NPs alone.

Aluminum Hydroxide Nano- and Microstructures Fabricated Using Scanning Probe Lithography with KOH Ink.

Using scanning probe lithography (SPL) with KOH ink, this study fabricates aluminum hydroxide (Al(OH)3) nano- and microfeatures on a gold (Au) film that has been deposited on an aluminum (Al) layer. Hydroxyl ions (OH-) from the KOH ink loaded onto the Au film can react with the underlying Al layer to form Al(OH)3 structures due to the decrease in the pH of the reacting solution.1 In this process, Al(OH)3 solidification is governed by the pH of the KOH ink solution, which is affected by its volume. Suitably small volumes (down to hundreds of attoliters) of the KOH ink solution can be applied to the substrate surface using dip-pen nanolithography (DPN) and polymer-pen lithography (PPL). Using DPN and PPL printing with the solid (i.e., gel) and liquid phases of KOH ink, sub-micron- (minimum ≈300 nm) and micron-sized (≥4 µm) Al(OH)3 features can be obtained, respectively. The fabrication of Al(OH)3 structures using the proposed pH-dependent solidification process can be achieved with relatively small volumes in ambient conditions without requiring a previously reported molding process.1,2.

Mass Fabrication of 3D Silicon Nano-/Microstructures by Fab-Free Process Using Tip-Based Lithography.

Methods for the mass fabrication of 3D silicon (Si) microstructures with a 100 nm resolution are developed using scanning probe lithography (SPL) combined with metal-assisted chemical etching (MACE). Protruding Si structures, including Si nanowires of over 10 µm in length and atypical shaped Si nano- and micropillars, are obtained via the MACE of a patterned gold film (negative tone) on Si substrates by dip-pen nanolithography (DPN) with polymer or by nanoshaving alkanethiol self-assembled monolayers (SAMs). Furthermore, recessed Si structures with arbitrary patterning and channels less than 160 nm wide and hundreds of nanometers in depth are obtained via the MACE of a patterned gold film (positive tone) on Si substrates by alkanethiol DPN. As an example of applications using protruded Si structures, nanoimprinting in an area of up to a centimeter is demonstrated through 1D and 2D SPL combined with MACE. Similarly, submicrometer polydimethylsiloxane (PDMS) stamps are employed over millimeter-scale areas for applications using recessed Si structures. In particular, the mass production of arbitrarily shaped Si microparticles at submicrometer resolution is developed using silicon-on-insulator substrates, as demonstrated using optical microresonators, surface-enhanced Raman scattering templates, and smart microparticles for fluorescence signal coding.

Fabrication of diffraction gratings by top-down and bottom-up approaches based on scanning probe lithography.

Generation of diffraction gratings by top-down and bottom-up approaches based on scanning probe lithography is demonstrated. With regard to top-down fabrication, silicon nanostructured diffraction gratings are fabricated through one-dimensional (1D) dip-pen-nanolithography (DPN). Nanodot arrays (two-dimensional simple cubic lattice) of alkanethiol self-assembled monolayers (SAMs) are printed by 1D DPN on an Au-film-coated silicon substrate with lattice distances of 700, 1000, and 1200 nm. Silicon nanocircular pillars of length hundreds of nanometers are generated by sequential Au etching and reactive ion etching (RIE) of the 1D DPN printed sample. The performance of the silicon diffraction gratings as a microspectrometer is demonstrated through red, green, and blue color diffraction with white light incident at 45°. Moreover, arrays of zirconia nanoparticles (NPs) with an average diameter of visible wavelength (φ ≈ 470 nm) on an Au substrate are generated via bottom-up fabrication of the diffraction gratings. Microarrays of hydrophilic alkanethiol SAMs are obtained by polymer pen lithography (PPL). Self-assembly of zirconia NPs occurs after the passivation of hydrophobic alkanethiol SAMs of the PPL-printed sample. Fraunhofer diffraction with a square aperture is observed for the zirconia NP diffraction grating fabricated by the bottom-up approach.