Matthew T. Shaw

Sub-10 nm Feature Size PS-b-PDMS Block Copolymer Structures Fabricated by a Microwave-Assisted Solvothermal Process

Block copolymer (BCP) microphase separation at surfaces might enable the generation of substrate features in a scalable, manufacturable, bottom-up fashion provided that pattern structure, orientation, alignment can be strictly controlled. A further requirement is that self-assembly takes place within periods of the order of minutes so that continuous manufacturingprocesses do not require lengthy pretreatments and sample storageleading to contamination and large facility costs. We report here microwave-assisted solvothermal (in toluene environments) self-assembly and directed self-assembly of a very low molecular weight cylinder-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) BCP on planar and patterned silicon nitride (Si3N4) substrates. Good pattern ordering was achieved in the order of minutes. Factors affecting BCP self-assembly, notably anneal time and temperature were studied and seen to have significant effects. Graphoepitaxy to direct self-assembly in the BCP yielded promising results producing BCP patterns with long-range translational alignment commensurate with the pitch period of the topographic patterns. This rapid BCP ordering method is consistent with the standard thermal/solvent anneal processes.

A general method for controlled nanopatterning of oxide dots: a microphase separated block copolymer platform

We demonstrate a facile, generic method for the fabrication of highly dense long range hexagonally ordered various inorganic oxide nanodots on different substrates by using a microphase separated polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film as a structural template. The method does not require complex co-ordination chemistry (between metal precursors and the polymer) and instead involves the simple, solution based chemistry applicable to a wide range of systems. A highly ordered PS-b-PEO thin film with perpendicularly oriented PEO cylinders is fabricated by solvent annealing over wafer scale. PEO cylinders are activated by ethanol to create a functional chemical pattern for nanodot development via spin coating and block selective metal ion inclusion. Subsequent UV/ozone treatment forms an ordered arrangement of oxide nanodots and removes the polymer components. The phase purity, crystallinity and thermal stability of these materials coupled to the ease of production may make them useful in technological applications. This method is particularly useful because the feature sizes can be tuned by changing the concentration of the precursors without changing the molecular weight and concentration of the block copolymer.

Study on the combined effects of solvent evaporation and polymer flow upon block copolymer self-assembly and alignment on topographic patterns.

Microphase separation of a polystyrene-block-polyisoprene-block-polystyrene triblock copolymer thin film under confined conditions (i.e., graphoepitaxy) results in ordered periodic arrays of polystyrene cylinders aligned parallel to the channel side-wall and base in a polyisoprene matrix. Polymer orientation and translational ordering with respect to the topographic substrate were elucidated by atomic force microscopy (AFM) while film thickness and polymer profile within the channel were monitored by cross-sectional transmission electron microscopy (TEM) as a function of time over a 6 h annealing period at 120 degrees C. Upon thermal annealing, the polymer film simultaneously undergoes three processes: microphase separation, evaporation of trapped solvent, and mass transport of polymer from the mesas into the channels. A significant volume of solvent is trapped within the polymer film upon spin coating arising from the increased polymer/substrate interfacial area due to the topographic pattern. Mass transport of polymer during this process results in nonuniform films, where subtle changes in the film thickness within the channel have profound effects on the microphase separation process. The initially disordered structure within the film underwent an orientation transition via an intermediate formation of perpendicular cylinders (nonequilibrium) to a parallel (equilibrium) orientation with respect to the channel base. Herein, we present a time-resolved study of the cylinder reorientation process detailing how changing film thickness during the annealing process dramatically affects both the local and lateral orientation of the observed structure. Finally, a brief mathematical model is provided to evaluate spin coating over a complex topography following a classical asymptotic approximation of the Navier-Stokes equations for the as-deposited films.

Orientation and Alignment Control of Microphase-Separated PS-b-PDMS Substrate Patterns via Polymer Brush Chemistry

Block copolymer (BCP) microphase separation at substrate surfaces might enable the generation of substrate features in a scalable, bottom-up fashion, provided that the pattern structure, orientation, and alignment can be strictly controlled. The PS-b-PDMS (polystyrene-b-polydimethylsiloxane) system is attractive because it can form small features and the two blocks can be readily differentiated during pattern transfer. However, PS-b-PDMS offers a considerable challenge, because of the chemical differences in the blocks, which leads to poor surface wetting, poor pattern orientation control, and structural instabilities. These challenges are considerably greater when line patterns must be created, and this is the focus of the current work. Here, we report controlled pattern formation in cylinder-forming PS-b-PDMS by anchoring different types of hydroxyl-terminated homopolymer and random copolymer brushes on planar and topographically patterned silicon substrates for the fabrication of nanoscale templates. It is demonstrated that non-PDMS-OH-containing brushes may be used, which offers an advantage for substrate feature formation. To demonstrate the three-dimensional (3-D) film structure and show the potential of this system toward applications such as structure generation, the PDMS patterns were transferred to the underlying substrate to fabricate nanoscale features with a feature size of ~14 nm.

Molecularly Functionalized Silicon Substrates for Orientation Control of the Microphase Separation of PS-b-PMMA and PS-b-PDMS Block Copolymer Systems

The use of block copolymer (BCP) thin films to generate nanostructured surfaces for device and other applications requires precise control of interfacial energies to achieve the desired domain orientation. Usually, the surface chemistry is engineered through the use of homo- or random copolymer brushes grown or attached to the surface. Herein, we demonstrate a facile, rapid, and tunable approach to surface functionalization using a molecular approach based on ethylene glycol attachment to the surface. The effectiveness of the molecular approach is demonstrated for the microphase separation of PS-b-PMMA and PS-b-PDMS BCPs in thin films and the development of nanoscale features at the substrate.

Surface-directed dewetting of a block copolymer for fabricating highly uniform nanostructured microdroplets and concentric nanorings.

Through a combination of nanoimprint lithography and block copolymer self-assembly, a highly regular dewetting process of a symmetric diblock copolymer occurs whereby the hierarchal formation of microdroplets and concentric nanorings emerges. The process is driven by the unique chemical properties and geometrical layout of the underlying patterned silsesquioxane micrometer-sized templates. Given the presence of nonpreferential substrate-polymer interactions, directed dewetting was utilized to produce uniform arrays of microsized droplets of microphase separated polystyrene-block-poly(methyl methylacrylate) (PS-b-PMMA), following thermal annealing at 180 °C. Microdroplets with diameters greater than 400 nm exhibited a hexagonal close-packed arrangement of nanodots on the surface with polydomain ordering. At the droplet periphery, the polydomain ordering was severely disrupted because of a higher in-plane radius of curvature. By reducing the droplet size, the in-plane radius of curvature of the microdroplet becomes significant and the PMMA cylinders adopt parallel structures in this confined geometry. Continuous scaling of the droplet results in the generation of isolated, freestanding, self-aligned, and self-supported oblique nanorings (long axis ∼250-350 nm), which form as interstitial droplets between the larger microdroplets. Optical and magnetic-based nanostructures may benefit from such hierarchal organization and self-supporting/aligned nanoring templates by combining more than one lithography technique with different resolution capabilities.

Fabrication of ordered, large scale, horizontally-aligned si nanowire arrays based on an in situ hard mask block copolymer approach.

A simple technique is demonstrated to fabricate horizontal, uniform, and hexagonally arranged Sinanowire arrays with controlled orientation and density at spatially well defined locations on a substrate based on an in situ hard-mask pattern-formation approach by microphase-separated block-copolymer thin films. The technique may have significant application in the manufacture of transistor circuitry.

Size and space controlled hexagonal arrays of superparamagnetic iron oxide nanodots: magnetic studies and application.

Highly dense hexagonally arranged iron oxide nanodots array were fabricated using PS-b-PEO self-assembled patterns. The copolymer molecular weight, composition and choice of annealing solvent/s allows dimensional and structural control of the nanopatterns at large scale. A mechanism is proposed to create scaffolds through degradation and/or modification of cylindrical domains. A methodology based on selective metal ion inclusion and subsequent processing was used to create iron oxide nanodots array. The nanodots have uniform size and shape and their placement mimics the original self-assembled nanopatterns. For the first time these precisely defined and size selective systems of ordered nanodots allow careful investigation of magnetic properties in dimensions from 50 nm to 10 nm, which delineate the nanodots are superparamagnetic, well-isolated and size monodispersed. This diameter/spacing controlled iron oxide nanodots systems were demonstrated as a resistant mask over silicon to fabricate densely packed, identical ordered, high aspect ratio silicon nanopillars and nanowire features.

Fabrication of highly ordered sub-20 nm silicon nanopillars by block copolymer lithography combined with resist design

The control of order and orientation of the self-assembly of cylinder-forming poly(styrene-b-dimethylsiloxane) block copolymer is demonstrated. Copolymer thin films are spun-cast onto topographically patterned (well-defined rectangular cross-section channels) polyhedral-silsesquioxane-type resist templates and annealed in solvent vapor. The templates used here are fabricated by UV-curing nanoimprint lithography and the surface properties of the resist are tuned by the ligands coordinated to the resists silsesquioxane cages. Depending on the resists composition and on the surface chemistry at the base of the trench (resist or silicon), various morphologies and orientations of the polydimethylsiloxane cylinders are observed without the use of a brush layer. Some surfaces are demonstrated to be neutral for the copolymer, without any wetting layer and, under favorable conditions, highly ordered features are observed over substrate areas of about 1 cm2 (scalable to larger surfaces). Also, the possibility of using solvents widely accepted in industry for polymer spin-coating and annealing is proved. Due to the high plasma etch resistance of the polydimethylsiloxane block, self-assembled patterns can be transferred to the silicon substrate producing silicon features with aspect ratios up to 2. We demonstrate that the methodology developed here could be integrated into conventional fabrication processes and scaled to wafer production.

Fabrication of a sub-10 nm silicon nanowire based ethanol sensor using block copolymer lithography

This paper details the fabrication of ultrathin silicon nanowires (SiNWs) on a silicon-on-insulator (SOI) substrate as an electrode for the electro-oxidation and sensing of ethanol. The nanowire surfaces were prepared by a block copolymer (BCP) nanolithographic technique using low molecular weight symmetric poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) to create a nanopattern which was transferred to the substrate using plasma etching. The BCP orientation was controlled using a hydroxyl-terminated random polymer brush of poly(styrene)-random-poly(methyl methacrylate) (HO-PS-r-PMMA). TEM cross-sections of the resultant SiNWs indicate an anisotropic etch process with nanowires of sub-10 nm feature size. The SiNWs obtained by etching show high crystallinity and there is no evidence of defect inclusion or amorphous region production as a result of the pattern transfer process. The high density of SiNWs at the substrate surface allowed the fabrication of a sensor for cyclic voltammetric detection of ethanol. The sensor shows better sensitivity to ethanol and a faster response time compared to widely used polymer nanocomposite based sensors.