Here, we show a facile and versatile method to prepare highly ordered inorganic patterns on solid substrates by pyrolyzing UV cross-linked polymer/functional precursor hybrid films. The crosslinked polymer matrix acted as structure-directing agent in a pyrolyzing process, whereas the functional precursor was converted into the skeleton of the micropatterns. The inorganic micropatterns could be further catalytically functionalized to grow CNT and ZnO nanorod arrays by simply changing different functional precursors. This simple technique offers new prospects in the field of micropatterns, nanolithography, and template.

Patterning is of paramount importance in many areas of modern science and technology. As a valuable part in miniaturized devices, large-scale aligned CNTs with serial port configuration is highly desirable. Here, we reported that the synthesis of a pair of patterned carbon nanotubes with the shape of serial port by CVD starting from different breath figure templates, cross-linked polymer matrix and ferrous inorganic micropatterns. The growth mechanism of the isolated CNT bundles is attributed to the selectively interfacial aggregation of the ferrocene to the walls of the cavities, a so-called Pickering-emulsion effect, whereas the honeycomblike skeleton of the dense CNT arrays develop from the catalytically functionalized hexagonal edges. This synthesis strategy exemplifies a new possibility for making use of CNTs to fabricate functional carbons with unique geometry or specific properties in a controllable way. We expect that the methodology can be also applied onto the fabrication of patterned graphene.

Multi-level carbon nanotube (CNT) arrays with adjustable patterns were prepared by a combination of the breath figure (BF) process and chemical vapor deposition. Polystyrene-b-poly(acrylic acid)/ferrocene was dissolved in carbon disulfide and cast onto a Si substrate covered with a transmission electron microscope grid in saturated relative humidity. A two-level microporous hybrid film with a block copolymer skeleton formed on the substrate after evaporation of the organic solvent and water. One level of ordered surface features originates from the contour of the hard templates; while the other level originates from the condensation of water droplets (BF arrays). Ultraviolet irradiation effectively cross-linked the polymer matrix and endowed the hybrid film with improved thermal stability. In the subsequent pyrolysis, the incorporated ferrocene in the hybrid film was oxidized and turned the polymer skeleton into the ferrous inorganic micropatterns. Either the cross-linked hybrid film or the ferrous inorganic micropatterns could act as a template to grow the multi-level CNT patterns, e.g. isolated and honeycomb-structured CNT bundle arrays perpendicular to the substrate.

Boron nitride nanotubes (BNNTs) are inappropriate for further chemical derivatization because of their chemical inertness. We demonstrate covalent activation of chemically inert BNNTs by isophorone diisocyanate (IPDI) to form isocyanate group (NCO)-terminated BNNT precursors with an 'NCO anchor' ready for further functionalization. As identified by Fourier transform infrared spectroscopy, a number of molecules or polymers with -COOH, -OH or -NH₂ groups are readily attached to the activated IPDI-BNNTs. The IPDI-BNNT-involving polymer composites have shown mechanical properties are considerably improved due to the good dispersibility of IPDI-BNNTs in the polymer matrix and the strong interfacial interactions between BNNTs and polymers. The methodology reported here provides a promising method to promote the chemical reactivity of BNNTs and covalently modify polymer nanocomposites with improved mechanical performance.

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