Nanoscopic Templates from Oriented Block Copolymer Films

Abstract

Polymers offer unique avenues for the structural control of materials on the nanoscopic length scale for the production of nanoporous media, membranes, lithographic templates, and scaffolds for assemblies of electronic materials.[1±4] With structures on this length scale, quantumproperties of electronic materials are exhibited even at elevated temperatures. The natural length scale of polymer chains and their morphologies in the bulk lie precisely at these length scales and, as such, there is a substantial effort to produce, characterize and use polymeric nanostructures. The ease of processing polymers adds to the attractiveness of polymer-based nanostructures. In comparison to the time-intensive process of sequential writing of nanoscale patterns, nanostructure formation by self-assembly is highly parallel and inherently fast. Block copolymers are ideal materials in this respect, since, due to the connectivity of two chemically distinct chains, the molecules self-assemble into ordered morphologies with a size scale limited to molecular dimensions. Of particular interest are block copolymers that form cylindrical microdomains, since the elimination of the minor component transforms the material into an array of nanopores. A prerequisite for the use of copolymers is the control over the orientation of the microdomains. In particular, for cylindrical microdomains, an orientation normal to the substrate surface is desirable. Two different approaches are used to this end. In thin films, random copolymers anchored to a substrate can be used to produce a neutral surface.[5] For entropic reasons, the microdomains orient normal to the substrate surface.[6] In a second approach, electric fields were used to orient the cylindrical microdomains parallel to the field lines.[7±10] The approach relies on the orientation-dependent polarization energy induced when an anisotropic body is placed in an electric field. An anisotropic microphase structure will orient such that the interfaces between the two blocks are aligned parallel to the electric field. In this article it is shown that cylindrical microdomains of a copolymer film can be used to generate an array of ordered nanoscopic pores with well-controlled size, orientation, and structure. To this end, selective etching procedures and a characterization of the samples by quantitative analysis of the X-ray scattering along with electron (EM) and atomic force microscopies (AFM) are described. The processes outlined are shown to be operative over a very large range in sample thickness ranging from 40 nm up to several micrometers. The resulting nanoporous films are promising candidates as membranes with specific transport properties and as templates for electronic and magnetic nanostructured materials.Figures 1A and 1B show AFM images obtained from a 40 nm±thick film prepared on a neutral substrate after annealing. Cylinders standing perpendicular to the substrate are clearly discernable, particularly in the phase image, since the height variations are very small. Polystyrene (PS...

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