Journal
ACS NANO
Volume 7, Issue 11, Pages 9961-9974Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nn403847z
Keywords
block copolymers; membranes; nanopores; solvent annealing; atomic layer deposition
Categories
Funding
- Natural Science Foundation of China [21004033, 21176120]
- National Basic Research Program of China [2011CB612302]
- Natural Science Research Program of the Jiangsu Higher Education Institutions [13KJA430005]
- Jiangsu Natural Science Funds for Distinguished Young Scholars [BK2012039]
- Fok Ying Dong Education Foundation [131046]
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Membranes with uniform, straight nanopores have important applications in diverse fields, but their application is limited by the lack of efficient producing methods with high controllability. In this work, we reported on an extremely simple and efficient strategy to produce such well-defined membranes. We demonstrated that neutral solvents were capable of annealing amphiphilic block copolymer (BCP) films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) with thicknesses up to 600 nm to the perpendicular orientation within 1 min. Annealing in neutral solvents was also effective to the perpendicular alignment of block copolymers with very high molecular weights, e.g., 362 000 Da. Remarkably, simply by immersing the annealed BCP films in hot ethanol followed by drying in air, the originally dense BCP films were nondestructively converted into porous membranes containing highly ordered, straight nanopores traversing the entire thickness of the membrane (up to 1.1 mu m). Grazing incident small-angle X-ray spectroscopy confirmed the hexagonal ordering of the nanopores over large areas. We found that the overflow of P2VP chains from their reservoir P2VP cylinders and the deformation of the PS matrix in the swelling process contributed to the transformation of the solid P2VP cylinders to empty straight pores. The pore diameters can be tuned by either changing the swelling temperatures or depositing thin layers of metal oxides on the preformed membranes via atomic layer deposition with a subnanometer accuracy. To demonstrate the application of the obtained porous membranes, we used them as templates and produced centimeter-scale arrays of aligned nanotubes of metal oxides with finely tunable wall thicknesses.
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