Elemental carbon materials exhibit unique electronic, mechanical, and chemical properties that make them attractive, for example, for nanoelectronic devices, [1] strengthenhancing materials, [2] separation media, [3][4][5][6] catalyst supports, [7] energy storage/conversion systems, [8] proximal probes, [9] optical components. [10] Well-defined nanoporous carbon materials are essential for a number of these applications. Ordered porous carbon materials have previously been replicated by using colloidal crystals [10] and presynthesized mesoporous silicas as scaffolds.[7] These methodologies are extremely difficult to adapt to the fabrication of large-scale ordered nanoporous films with controlled pore orientations. Although numerous methods (e.g., chemical vapor deposition, [11] ultrasonic deposition, [3a] silica template synthesis, [3b, 7] hydrothermal decomposition of carbide compounds, [12] and polymer coating and pyrolysis [13] ) have been developed for the fabrication of carbon films, no ordered nanoporous carbon films have been obtained with such methods. Accordingly, the large-scale alignment of the carbon nanostructural films is still a big challenge. Herein, we demonstrate a stepwise self-assembly approach to the preparation of large-scale, highly ordered nanoporous carbon films. The carbon precursor molecules are spatially arranged into well-defined nanostructures by the self-assembly of block copolymers (BCPs). A hexagonally packed carbon-channel array whose orientation is normal to the carbon film surface has been successfully synthesized. Large-scale crack-free carbon films of up to 6 cm 2 can be readily fabricated on common substrates such as silica, copper, silicon, and carbon.The self-assembly of BCPs has proven to be a versatile approach to the selective organization and nanoscale regulation of the concentration distribution of target molecular species for the fabrication of nanoporous materials. [14][15][16] The mechanism for such organization involves hydrogen-bonding, [17] ion-pairing, [18] and/or dative interactions [19] between supramolecular assemblies of BCPs and target molecular species. The resulting composites can give rise to various nanostructures according to the structural and phase behaviors of the BCPs. The target molecular species are spatially concentrated in selected microdomains and can eventually serve as nanostructured catalysts, [20] spacers, [21] or precursors [22] for the further fabrication of ordered nanostructures. Highly ordered nanoporous materials, such as polymer, [22] silica, [23,24] and organic-inorganic hybrid materials, [25,26] have been created through polymerization in the presence of the self-assembled BCPs.Although BCPs contain high atomic carbon concentrations, ordered nanoporous carbon films have not been successfully fabricated through the direct pyrolysis of selfassembled BCPs.[27] This inability is attributed to the fact that linearly structured BCP compounds have very poor carbon yields in carbonization reactions. Furthermore, the survival of the nan...
