Nanometer-scale patterns have been created in self-assembled monolayers by using a scanning near-field optical microscope coupled to an ultra-violet laser emitting light at a wavelength of 244 nm. Sharp, chemically well-defined features with dimensions as small as 40 nm have been created routinely, and on occasions line widths of 25 nm (lambda/10) have been achieved. Because of the wide range of photochemical methods available for surface derivatization, this approach promises to provide a flexible and versatile route to the generation of molecular and biological nanostructures for a wide range of applications.

The UV photo-oxidation of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) has been studied using static secondary ion mass spectrometry, X-ray photoelectron spectroscopy, contact angle measurement, and friction force microscopy. OEG-terminated SAMs are oxidized to yield sulfonates, but photodegradation of the OEG chain also occurs on a more rapid time scale, yielding degradation products that remain bound to the surface via gold-sulfur bonds. The oxidation of these degradation products is the rate-limiting step in the process. Photopatterning of OEG-terminated SAMs may be accomplished by using a mask and suitable light source or by using scanning near-field photolithography (SNP) in which the mask is replaced by a scanning near-field optical microscope coupled to a UV laser. Using SNP, it is possible to fabricate patterns in SAMs with a full width at half-maximum height (fwhm) as small as 9 nm, which is approximately 15 times smaller than the conventional diffraction limit. SNP-patterned OEG-terminated SAMs may be used to fabricate protein nanopatterns. By adsorbing carboxylic acid-terminated thiols into oxidized regions and converting these to active ester intermediates, it has been possible to fabricate lines of protein molecules with widths of only a few tens of nanometers.

Friction force microscopy (FFM) is a technique based upon scanning force microscopy that provides information on the properties of molecular materials. Continuum mechanics provides models that may be used to conduct quantitative analyses of data. While there are some important unresolved issues associated with the contact mechanics of the tip-sample interaction, there is a growing body of data that demonstrates the sensitivity of FFM to changes in molecular organisation and surface composition. Importantly, FFM provides these data with nm spatial resolution, making it in many respects a unique tool for exploring the structures of organic materials on small length scales. Some of the capabilities of FFM are illustrated by drawing on both the literature and work performed in the authors' laboratory on self-assembled monolayers. For example, the compositions of mixed monolayer systems may be determined, with control of tip chemistry providing an additional element of chemical specificity; the alkyl chain organisation may be investigated; and the rates of surface chemical reactions may be measured. FFM is a powerful tool for the quantitative investigation of nm scale chemistry.

Directed self-assembly of nanoparticles (DSA-n) holds great potential for device miniaturization in providing patterning resolution and throughput that exceed existing lithographic capabilities. Although nanoparticles excel at assembling into regular close-packed arrays, actual devices on the other hand are often laid out in sparse and complex configurations. Hence, the deterministic positioning of single or few particles at specific positions with low defect density is imperative. Here, we report an approach of DSA-n that satisfies these requirements with less than 1% defect density over micrometer-scale areas and at technologically relevant sub-10 nm dimensions. This technique involves a simple and robust process where a solvent film containing sub-10 nm gold nanoparticles climbs against gravity to coat a prepatterned template. Particles are placed individually into nanoscale cavities, or between nanoposts arranged in varying degrees of geometric complexity. Brownian dynamics simulations suggest a mechanism in which the particles are pushed into the template by a nanomeniscus at the drying front. This process enables particle-based self-assembly to access the sub-10 nm dimension, and for device fabrication to benefit from the wealth of chemically synthesized nanoparticles with unique material properties.

The wettability and evaporation of water-ethanol binary droplets on the substrate with micropyramid cavities are studied by controlling the initial ethanol concentrations. The droplets form octagonal initial wetting areas on the substrate. As the ethanol concentration increases, the side ratio of the initial wetting octagon increases from 1.5 at 0% ethanol concentration to 3.5 at 30% ethanol concentration. The increasing side ratio indicates that the wetting area transforms from an octagon to a square if we consider the octagon to be a square with its four corners cut. The droplets experience a pinning-depinning transition during evaporation. The pure water sessile droplet evaporation demonstrates three stages from the constant contact line (CCL) stage, and then the constant contact angle (CCA) stage, to the mixed stage. An additional mixed stage is found between the CCL and CCA stages in the evaporation of water-ethanol binary droplets due to the anisotropic depinning along the two different axes of symmetry of the octagonal wetting area. Droplet depinning occurs earlier on the patterned surface as the ethanol concentration increases.

The advancement of molecular nanotechnology requires new tools for the characterization of surface chemical reactivity with nanometer spatial resolution. While spectroscopy on sub-100 nm length scales remains challenging, friction force microscopy (FFM) is a promising tool for the characterization of molecular materials, although to date it has been little used in studies of surface reactivity. Here we report the use of FFM to measure the kinetics of photo-oxidation of self-assembled monolayers (SAMs) of alkanethiols adsorbed on gold surfaces. Two alternative approaches (analysis of friction-load plots and the use of line sections through images of patterned materials) are compared and found to yield data in very good agreement, with rate constants being found to be in good agreement despite being carried out on different microscopes. The use of line-section analysis provides a convenient method for the quantification of the extent of reaction in nanometer-scale patterns created in SAMs by the novel approach of scanning near-field photolithography.

Self-assembled monolayers (SAMs) of alkanethiols have been patterned on micrometre and nanometre length scales by exposure to light from a frequency doubled argon ion laser. Friction force microscopy shows that the patterning speed depends on the nature of the terminal group and is in the order COOH> CH3, the reverse of the order reported previously using a mercury arc lamp, indicating that a different photo-oxidation mechanism is responsible. It is suggested that this involves the creation of hot electrons at the gold surface that initiate oxidation of the adsorbate. Nanostructures have been fabricated using scanning near-field photolithography (SNP), in which the UV laser is coupled to a near-field scanning optical microscope. During SNP, the rates of writing required for complete oxidation correlate closely with oxidation rates measured during micropatterning, suggesting that the mechanism is essentially the same. SAMs on silver have been patterned, yielding linewidths smaller than 50 nm. The selective alkylation of hydrogen passivated Si has been demonstrated, yielding structures that may be used as resists for etching and demonstrating a powerful new capability—fluid-phase nanophotolithography. Patterned SAMs prepared using SNP have been used to selectively attach polymer nanoparticles, demonstrating their utility for the creation of functional molecular nanostructures. Nanopatterns generated by SNP have also been used as resists, enabling the etching of nanostructures into gold and the fabrication of three-dimensional nanostructures in silicon using a two-stage wet etch process.

Nanostructures of metal sulfides are conventionally prepared via chemical techniques and patterned using self-assembly. This poses a considerable amount of challenge when arbitrary shapes and sizes of nanostructures are desired to be placed at precise locations. Here, we describe an alternative approach of nanoscale patterning of zinc sulfide (ZnS) directly using a spin-coatable and electron beam sensitive zinc butylxanthate resist without the lift-off or etching step. Time-resolved electron beam damage studies using micro-Raman and micro-FTIR spectroscopies suggest that exposure to a beam of electrons leads to quick disappearance of xanthate moieties most likely via the Chugaev elimination, and further increase of electron dose results in the appearance of ZnS, thereby making the exposed resist insoluble in organic solvents. Formation of ZnS nanocrystals was confirmed by high-resolution transmission electron microscopy and selected area electron diffraction. This property was exploited for the fabrication of ZnS lines as small as 6 nm and also enabled patterning of 10 nm dots with pitches as close as 22 nm. The ZnS patterns fabricated by this technique showed defect-induced photoluminescence related to sub-band-gap optical transitions. This method offers an easy way to generate an ensemble of functional ZnS nanostructures that can be arbitrarily patterned and placed in a precise way. Such an approach may enable programmable design of functional chalcogenide nanostructures.