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Polymer electrolyte membranes (PEMs) with high and controlled ionic conductivity are important for energy-related applications, such as solid-state batteries and fuel cells. Herein we disclose a new strategy to fabricate long-range ordered PEMs with tunable ion conducting pathways using a holographic polymerization (HP) method. By incorporating polymer electrolyte into the carefully selected HP system, electrolyte layers/channels with length scales of a few tens of nanometers to micrometers can be formed with controlled orientation and anisotropy; ionic conductivity anisotropy as high as 37 has been achieved., (© 2011 American Chemical Society)

Layered polymer/nanoparticle composites have been created through the one-step two-beam interference lithographic exposure of a dispersion of 25 and 50 nm silica particles within a photopolymerizable mixture at a wavelength of 532 nm. The polymerizable mixture is composed of pentaerythritol triacrylate (monomer), 1-vinyl-2-pyrrolidinone (monomer), and photoinitiator. In the areas of constructive interference, the monomer begins to polymerize via a free-radical process and concurrently the nanoparticles move into the regions of destructive interference. The effects of exposure time, power density, nanoparticle size, and periodicity on the final nanocomposite structure were measured with transmission electron microscopy to determine the mechanism for particle segregation. Diffraction from the sample was monitored as well, though its magnitude was not a good predictor of nanostructure in this relatively low index contrast system. Exposure time did not have a strong effect on the final structure. The best nanoparticle sequestration was observed at reduced laser power density, smaller interferogram periodicity, and decreased nanoparticle size, indicating that particle segregation is dominated by diffusion-limited nanoparticle transport directed by a matrix containing a gradient of polymerization kinetics.

We report the combination of top-down and bottom-up nanomanufacturing techniques to fabricate active, hierarchically structured volume reflection gratings. Holographic polymerization (H-P) formed lamellar structures of approximately 200 nm in thickness, confining a block copolymer (BCP) to approximately 100 nm domains. Subsequently, the BCP self-assembles into nanolayers with a period of approximately 21 nm. We envisage that this approach opens a gateway to fabricating hierarchical nanostructures at different length scales.