3D Nanostructured Conjugated Polymers for Optical Applications

This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/adfm.201502392The self assembly of block-copolymers into the gyroid morphology was replicated into 3D nanostructured conjugated polymers. Voided styrenic gyroidal networks were used as scaffolds for the electrodeposition of two poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives and poly(pyrrole) (PPy). The careful choice of solvents and electrolytes allowed the excellent replication of the initial self-assembled morphology into self-supporting gyroidal conjugated polymer networks. The nanostructured films were employed to fabricate electrochromic devices, exhibiting excellent colour contrast upon switching, with fast switching speeds. The versatility and reliability of this method was demonstrated by the creation of switchable Fresnel zone plates, with which the focussing of light can be switched on and off.We acknowledge the EPSRC EP/G060649/1 for funding. This study was supported by the Nokia Research Centre Cambridge

Synthesis and cryogenic spectroscopy of narrow-diameter single-wall carbon nanotubes

AbstractWe report chemical vapor deposition and cryogenic photoluminescence studies of narrow-diameter single-wall carbon nanotubes. Our systematic study of synthesis parameters identifies means to control the average length, diameter, and areal density of carbon nanotubes grown on silica substrates. Using synthesis conditions that favor the growth of carbon nanotubes with sub-nanometer diameters, we fabricate samples with spatially isolated suspended nanotubes ideally suited for optical studies. Photoluminescence spectroscopy of individual nanotubes reveals two classes: spectrally broad and narrow single-peak emission at the temperature of liquid helium. The latter class with spectral line widths down to the resolution limit of our spectrometer of 40 μeV indicates that exciton coherence in carbon nanotubes can be substantially improved by controlling the growth conditions and utilized in sources of indistinguishable single photons

Optical Imaging of Large Gyroid Grains in Block Copolymer Templates by Confined Crystallization.

Block copolymer (BCP) self-assembly is a promising route to manufacture functional nanomaterials for applications from nanolithography to optical metamaterials. Self-assembled cubic morphologies cannot, however, be conveniently optically characterized in the lab due to their structural isotropy. Here, the aligned crystallization behavior of a semicrystalline-amorphous polyisoprene-b-polystyrene-b-poly(ethylene oxide) (ISO) triblock terpolymer was utilized to visualize the grain structure of the cubic microphase-separated morphology. Upon quenching from a solvent swollen state, ISO first self-assembles into an alternating gyroid morphology, in the confinement of which the PEO crystallizes preferentially along the least tortuous pathways of the single gyroid morphology with grain sizes of hundreds of micrometers. Strikingly, the resulting anisotropic alignment of PEO crystallites gives rise to a unique optical birefringence of the alternating gyroid domains, which allows imaging of the self-assembled grain structure by optical microscopy alone. This study provides insight into polymer crystallization within a tortuous three-dimensional network and establishes a useful method for the optical visualization of cubic BCP morphologies that serve as functional nanomaterial templates.This research was supported through the Swiss National Science Foundation through grant numbers 163220 (U.S.) and 168223 (B.D.W.), the National Center of Competence in Research Bio-Inspired Materials (U.S., B.D.W, I.G.), the Adolphe Merkle Foundation (B.D.W., U.S., I.G.), the Engineering and Physical Sciences Research Council through the Cambridge NanoDTC EP/G037221/1, EP/L027151/1, EP/N016920/1, and EP/G060649/1 (R.D., J.A.D., J.J.B.), and ERC LINASS 320503 (J.J.B.). This project has also received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 706329/cOMPoSe (I.G.). Y.G. and U.W. thank the National Science Foundation (DMR-1409105) for financial support. Part of the work was conducted at beamline D1 at the Cornell High Energy Synchrotron Source (CHESS); CHESS is supported by the NSF and NIH/NIGMS via NSF award DMR-1332208. We also thank Diamond Light Source for access to beamline I22 (SM13448) that contributed to the results presented here

Halogen-Bond Driven Self-Assembly of Perfluorocarbon Monolayers

The self-assembly of a single layer of organic molecules on a substrate is a powerful strategy to modify surfaces and interfacial properties. The detailed interplay of molecule-to-substrate and molecule-molecule interactions are crucial for the preparation of stable and uniform monomolecular coatings. Thiolates, silanes, phosphonates and carboxylates are widely used head-groups to link organic molecules to specific surfaces study we show that self-assembly of stable and highly compact monolayers of perfluorocarbons. Remarkably, the lowest ever reported surface energy of 2.6 mJ m-2 was measured for a perfluorododecyl iodide monolayer on a silicon nitride substrate. As a convenient, flexible and simple method, the self-assembly of halogen-bond driven perfluorocarbon monolayers is compatible with several applications, ranging from biosensing to electronics and microfluidics. Compared to other methods used to functionalise surfaces and interfaces, our procedure offers the unique advantage to work with extremely inert perfluorinated solvents. We demonstrate that surfaces commonly unstable in contact with many common organic solvents, such as organic-inorganic perovskites, can be functionalized via halogen bonding