Nanoparticle assemblies in thin films of supramolecular nanocomposites.

We demonstrated a versatile approach to obtain layered nanoparticle sheets with in-plane hexagonal order and 3-D ordered arrays of single nanoparticle chains in thin films upon blending nanoparticles with block copolymer (BCP)-based supramolecules. Basic understanding on the thermodynamic and kinetic aspects of the assembly process paved a path to manipulate these assemblies to meet demands in nanoparticle-based device fabrication and understand structure-property correlations.

Templated self-assembly of square symmetry arrays from an ABC triblock terpolymer.

Self-assembly provides the ability to create well-controlled nanostructures with electronic or chemical functionality and enables the synthesis of a wide range of useful devices. Diblock copolymers self-assemble into periodic arrays of microdomains with feature sizes of typically 10-50 nm, and have been used to make a wide range of devices such as silicon capacitors and transistors, photonic crystals, and patterned magnetic media(1-3). However, the cylindrical or spherical microdomains in diblock copolymers generally form close-packed structures with hexagonal symmetry, limiting their device applications. Here we demonstrate self-assembly of square-symmetry patterns from a triblock terpolymer in which one organometallic block imparts high etch selectivity and etch resistance. Long-range order is imposed on the microdomain arrays by self-assembly on topographical substrates, and the orientation of both square lattices and in-plane cylinders is controlled by the substrate chemistry. Pattern transfer is demonstrated by making an array of square-packed 30 nm tall, 20 nm diameter silica pillars. Templated self-assembly of triblock terpolymers can generate nanostructures with geometries that are unattainable from diblock copolymers, significantly enhancing the capabilities of block copolymer lithography.

Nanoscale rings fabricated using self-assembled triblock terpolymer templates.

Although there has been extensive work on the use of self-assembled diblock copolymers for nanolithography, there are few reports of the use of multiblock copolymers, which can form a more diverse range of nanoscale pattern geometries. Pattern transfer from a self-assembled poly(butadiene-b-styrene-b-methyl methacrylate) (PB-b-PS-b-PMMA) triblock terpolymer thin film has been investigated. Polymers of different total molecular weight were synthesized with a predicted morphology consisting of PMMA-core/PS-shell cylinders in a PB matrix. By adjusting the solvent-annealing conditions and the film thickness, thin films with vertically oriented cylinders were formed. The PMMA cylinder cores and the PB matrix were then removed using selective etching to leave an array of PS rings, and the ring pattern was transferred into a silica film by reactive ion etching to form 19 nm high silica rings. This result illustrates the design and use of triblock terpolymers for self-assembled lithography.

Self-assembled one-dimensional nanostructure arrays.

A range of proposed devices relies on the electronic, optical or magnetic properties of one-dimensional (1D) chains of nanoparticles. Here, well-controlled 1D arrays have been formed by templating a spherical-morphology block copolymer within a narrow groove. Significantly, the domains are distorted into ellipses with aspect ratio and major axis orientation controlled by the groove width. This technique gives unprecedented control over the period, particle size, aspect ratio, and orientation of nanoparticles in 1D arrays, making it valuable for creating self-assembled masks for the fabrication of novel devices.

Three-dimensional self-assembly of spherical block copolymer domains into V-shaped grooves.

The self-assembly of a spherical-morphology block copolymer into V-shaped grooves has been investigated. Although spherical morphology block copolymers typically form a bcc sphere array in bulk, the V groove promotes the formation of a well-ordered fcc close-packed sphere array with the (111) planes of the array parallel to the groove walls. The sphere size in the block copolymer adjusts depending on the commensurability between the periodicity of the block copolymer and the film thickness within the V groove. The top surface of the close-packed array, parallel to the substrate, shows a square symmetry, unlike the hexagonal symmetry seen in monolayers of spherical domains, which may provide a useful geometry for block copolymer lithography.