Directed self-assembly of sub-10 nm particle clusters using topographical templates.

Directed self-assembly of nanoparticles (DSA-n) is an approach that creates suitable conditions to capture nanoparticles randomly dispersed in a liquid and position them into predefined locations on a solid template. Although DSA-n is emerging as a potential bottom-up patterning technique to build nanostructures using nanoparticles of various sizes, geometries and material compositions, there are still several outstanding challenges. In this paper, we focus on the DSA-n of sub-10 nm particles using topographical templates to guide them into 1D and 2D ordered arrays. The process mechanism leading DSA-n at sub-10 nm size scale has been reviewed and experimental evidence of the impact of the template on the positioning both individual and clusters of particles with low level of structure defects have also been demonstrated. Furthermore, by controlling the drying direction of the liquid within polygonal traps, we are also able to tune the spacing between the trapped nanoparticle clusters. This self-structuring phenomenon is of crucial importance for various applications such as plasmonics and charge transport within quantum circuits, whereby the coupling effects are highly dependent on the size of the nanoparticles and their separation.

Large Area Directed Self-Assembly of Sub-10 nm Particles with Single Particle Positioning Resolution.

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.

Room-Temperature Patterning of Nanoscale MoS2 under an Electron Beam.

Molybdenum disulfide (MoS2) is traditionally grown at a high temperature and subsequently patterned to study its electronic properties or make devices. This method imposes severe limitations on the shape and size of MoS2 crystals that can be patterned precisely at required positions. Here, we describe a method of direct nanoscale patterning of MoS2 at room temperature by exposing a molybdenum thiocubane single-source precursor to a beam of electrons. Molybdenum thiocubanes with various alkylxanthate moieties [Mo4S4(ROCS2)6, where R = alkyl] were prepared using a "self-assembly" approach. Micro-Raman and micro-FTIR spectroscopic studies suggest that exposure to a relatively smaller dose of electrons results in the breakdown of xanthate moieties, leading to the formation of MoS2. High-resolution transmission electron micrographs suggest that the growth of MoS2 most likely happens along (100) planes. An electron-beam-induced chemical transformation of a molybdenum thiocubane resist was exploited to fabricate sub-10 nm MoS2 lines and dense dots as small as 13 nm with a pitch of 33 nm. Since this technique does not require the liftoff and etching steps, patterning of MoS2 with interesting shapes, sizes, and thicknesses potentially leading to tunable band gap is possible.

Ultrasmall Designed Plasmon Resonators by Fused Colloidal Nanopatterning.

This work presents a procedure for large-area patterning of designed plasmon resonators that are much smaller than possible with conventional lithography techniques. Fused Colloidal Nanopatterning combines directed self-assembly and controlled fusing of spherical colloidal nanoparticles. The two-step approach first patterns a surface covered with hydrogen silsesquioxane, an electron beam resist, forming traps into which the colloidal gold nanoparticles self-assemble. Second, the patterned nanoparticles are controllably fused to form plasmon resonators of any 2D designed shape. The heights and widths of the plasmon resonators are determined by the diameter of the nanoparticle building blocks, which can be well below 10 nm. By performing the fusing step with UV ozone and heat exposure, we demonstrate that the process is easily scalable to cover large areas on silicon wafers with designed gold nanostructures. The procedure neither requires adhesion layers nor a lift-off process, making it ideally suited for plasmonics, in comparison with regular electron beam lithography. We use monochromated electron energy loss spectroscopy (EELS) in scanning transmission electron microscopy and boundary element method simulations to demonstrate that the designed plasmon resonators are directly tunable via the pattern design. We foresee future expansion of this approach for applications such as plasmon-enhanced photocatalysis and for large-scale patterning where chemical, optical, or confinement properties require sub-10 nm metal lines.

Non-invasive paper-based microfluidic device for ultra-low detection of urea through enzyme catalysis.

This work describes the design, fabrication and characterization of a paper-based microfluidic device for ultra-low detection of urea through enzyme catalysis. The microfluidic system comprises an entry port, a fluidic channel, a reaction zone and two electrodes (contacts). Wax printing was used to create fluidic channels on the surface of a chromatography paper. Pre-conceptualized designs of the fluidic channel are wax-printed on the paper substrate while the electrodes are screen-printed. The paper printed with wax is heated to cause the wax reflow along the thickness of the paper that selectively creates hydrophilic and hydrophobic zones inside the paper. Urease immobilized in the reaction zone catalyses urea into releasing ions and, thereby, generating a current flow between the electrodes. A measure of current with respect to time at a fixed potential enables the detection of urea. The methodology enabled urea concentration down to 1 pM to be detected. The significance of this work lies in the use of simple and inexpensive paper-based substrates to achieve detection of ultra-low concentrations of analytes such as urea. The process is non-invasive and employs a less cumbersome two-electrode assembly.

Second order directed positioning of nanoparticles induced by the main terminal meniscus shape in irregular template cavities.

Directed self-assembly of nanoparticles using topographical templates has demonstrated great capabilities of ordering particles at their maximum packing fraction resulting from template confinement effects and free energy minimization. However, to self-assemble nanostructures at a lower packing fraction with a precise control over particle's positioning is challenging due to the high entropy of such a system. Here, by fabricating templates of irregular cavities together with appropriate choice of solvent, we demonstrate the positioning of 8 nm Au nanoparticles within individual cavities at a low filling factor. In addition to the first-order of ordering dictated by the template topography, there is a second-order of ordering induced by the interplay between the evaporation of the residual solvent trapped within the cavities and their intrinsic geometries. The experimental results show that the cavities shaped as equilateral triangles exhibit a random positioning of the particles at the corners; in comparison, right-angled scalene (or irregular) triangles show a more controllable positioning of the particles within the corners of the smallest angle. Finally, this technique has been successfully used to fabricate arrays of dimers with a controllable center-to-center distances at sub-5 nm length scales.

Direct Patterning of Zinc Sulfide on a Sub-10 Nanometer Scale via Electron Beam Lithography.

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.

Fabrication of Self-Cleaning, Reusable Titania Templates for Nanometer and Micrometer Scale Protein Patterning.

The photocatalytic self-cleaning characteristics of titania facilitate the fabrication of reuseable templates for protein nanopatterning. Titania nanostructures were fabricated over square centimeter areas by interferometric lithography (IL) and nanoimprint lithography (NIL). With the use of a Lloyd's mirror two-beam interferometer, self-assembled monolayers of alkylphosphonates adsorbed on the native oxide of a Ti film were patterned by photocatalytic nanolithography. In regions exposed to a maximum in the interferogram, the monolayer was removed by photocatalytic oxidation. In regions exposed to an intensity minimum, the monolayer remained intact. After exposure, the sample was etched in piranha solution to yield Ti nanostructures with widths as small as 30 nm. NIL was performed by using a silicon stamp to imprint a spin-cast film of titanium dioxide resin; after calcination and reactive ion etching, TiO2 nanopillars were formed. For both fabrication techniques, subsequent adsorption of an oligo(ethylene glycol) functionalized trichlorosilane yielded an entirely passive, protein-resistant surface. Near-UV exposure caused removal of this protein-resistant film from the titania regions by photocatalytic degradation, leaving the passivating silane film intact on the silicon dioxide regions. Proteins labeled with fluorescent dyes were adsorbed to the titanium dioxide regions, yielding nanopatterns with bright fluorescence. Subsequent near-UV irradiation of the samples removed the protein from the titanium dioxide nanostructures by photocatalytic degradation facilitating the adsorption of a different protein. The process was repeated multiple times. These simple methods appear to yield durable, reuseable samples that may be of value to laboratories that require nanostructured biological interfaces but do not have access to the infrastructure required for nanofabrication.

Fabrication of biomolecular nanostructures by scanning near-field photolithography of oligo(ethylene glycol)-terminated self-assembled monolayers.

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.

Measurement of the kinetics of photo-oxidation of self-assembled monolayers using friction force microscopy.

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.

Friction force microscopy: towards quantitative analysis of molecular organisation with nanometre spatial resolution.

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.

Nanoscale molecular patterns fabricated by using scanning near-field optical lithography.

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.