Self-assembling materials spontaneously form structures at length scales of interest in nanotechnology. In the particular case of block copolymers, the thermodynamic driving forces for self-assembly are small, and low-energy defects can get easily trapped. We directed the assembly of defect-free arrays of isolated block copolymer domains at densities up to 1 terabit per square inch on chemically patterned surfaces. In comparing the assembled structures to the chemical pattern, the density is increased by a factor of four, the size is reduced by a factor of two, and the dimensional uniformity is vastly improved.

Self-assembling block copolymers are of interest for nanomanufacturing due to the ability to realize sub-100 nm dimensions, thermodynamic control over the size and uniformity and density of features, and inexpensive processing. The insertion point of these materials in the production of integrated circuits, however, is often conceptualized in the short term for niche applications using the dense periodic arrays of spots or lines that characterize bulk block copolymer morphologies, or in the long term for device layouts completely redesigned into periodic arrays. Here we show that the domain structure of block copolymers in thin films can be directed to assemble into nearly the complete set of essential dense and isolated patterns as currently defined by the semiconductor industry. These results suggest that block copolymer materials, with their intrinsically advantageous self-assembling properties, may be amenable for broad application in advanced lithography, including device layouts used in existing nanomanufacturing processes.

Lamellae-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films, with bulk period L 0, were directed to assemble on lithographically nanopatterned surfaces. The chemical pattern was comprised of “guiding” stripes of cross-linked polystyrene (X-PS) or poly(methyl methacrylate) (X-PMMA) mats, with width W, and interspatial “background” regions of a random copolymer brush of styrene and methyl methacrylate (P(S-r-MMA)). The fraction of styrene (f) in the brush was varied to control the chemistry of the background regions. The period of the pattern was L s. After assembly, the density of the features (domains) in the block copolymer film was an integer multiple (n) of the density of features of the chemical pattern, where n = L s/L 0. The quality of the assembled PS-b-PMMA films into patterns of dense lines as a function of n, W/L 0, and f was analyzed with top-down scanning electron microscopy. The most effective background chemistry for directed assembly with density multiplication corresponded to a brush chemistry (f) that minimized the interfacial energy between the background regions and the composition of the film overlying the background regions. The three-dimensional structure of the domains within the film was investigated using cross-sectional SEM and Monte Carlo simulations of a coarse-grained model and was found most closely to resemble perpendicularly oriented lamellae when W/L 0 ∼ 0.5–0.6. Directed self-assembly with density multiplication (n = 4) and W/L 0 = 1 or 1.5 yields pattern of high quality, parallel linear structures on the top surface of the assembled films, but complex, three-dimensional structures within the film.

A coarse grain model and a Monte Carlo sampling formalism are proposed for simulations of self-assembly in block copolymer melts and nanoparticle−copolymer composites. Our approach relies on a particle-based representation of the system, it does not invoke a saddle point approximation, and it permits treatment of large three-dimensional systems. We provide a detailed description of the model and methods and discuss their relationship to results from self-consistent-field theory and single chain in mean field simulations. The validity of the proposed approach is addressed by applying it to study systems whose description within existing approaches would be demanding. In particular, we use it to examine the directed assembly of copolymer blends and nanoparticles on nanopatterned substrates. We show that results from simulations are in good agreement with experiment, and we use our theoretical findings to help explain the experimental observations.

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We investigate the assembly of block copolymer-nanoparticle composite films on chemically nanopatterned substrates and present fully three-dimensional simulations of a coarse grain model for these hybrid systems. The location and distribution of nanoparticles within the ordered block copolymer domains depends on the thermodynamic state of the composite in equilibrium with the surface. Hierarchical assembly of nanoparticles enables applications in which the ability to precisely control their locations within periodic and nonregular geometry patterns and arrays is required.

We present a control strategy for the facile placement of densely packed nanomaterial arrays (i.e., nanoparticles and nanorods) on surface reconstructed polystyrene-block-poly(methyl methacrylate) thin film patterns. The surface reconstruction of perpendicularly oriented block copolymer thin films, which were produced by a treatment with selective solvent vapors for both blocks, created the topographical nanopatterns with enough height contrast for nanoparticle deposition without the need for additional selective etching of a single block domain. The deposition method of nanomaterials was also optimized, and densely packed one- and two-dimensional nanomaterials arrays in the grooves of the block copolymer film patterns were fabricated efficiently. Then, we demonstrated that height contrast of the surface reconstructed block copolymer films could be reversed by electron beam irradiation resulting in nanomaterial arrays placed at the mesa phase of the nanopatterns. On the basis of this nanomaterial placement control strategy, dual nanomaterial arrays on a single block copolymer pattern were also realized.

The reaction of end-functionalized polymer chains at the melt interface between the immiscible polymers, polystyrene (PS) and poly(2-vinylpyridine) (P2VP), has been investigated experimentally. Diblock copolymers were formed at the interface by the reaction of amine end-functionalized deuterated PS with anhydride end-functionalized P2VP. The normalized interfacial excess (ξ = z*PS/R g,PS) of the deuterium-labeled block copolymer was determined using dynamic secondary ion mass spectrometry (DSIMS). As ξ increases, the interfacial tension decreases to zero, at which point the interface becomes unstable, inducing interfacial roughening by hydrodynamic flow of the homopolymers. Roughening was detected using scanning force microscopy (SFM) after removing the polystyrene with a selective solvent. Evidence of the interfacial instability was also observed by cross-sectional transmission electron microscopy (TEM). The length scale of the corrugation was around 15 nm, which was comparable to the diameter of diblock copolymer emulsified droplets found near the interface. For a short symmetric block copolymer (PS (4K)−P2VP (4K)), we observed that the interfacial roughening takes place above ξ = 0.9, in good agreement with the predictions of self-consistent mean-field theory.