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Edwin L Thomas

Publications and source records attributed to Edwin L Thomas.

17 recordsLinked to original sources
PubMed2006

Mechanically tunable three-dimensional elastomeric network/air structures via interference lithography.

We show how to employ an interference lithographic template (ILT) as a facile mold for fabricating three-dimensional bicontinuous PDMS (poly(dimethylsiloxane)) elastomeric structures and demonstrate the use of such a structure as a mechanically tunable PDMS/air phononic crystal. A positive photoresist was used to make the ILT, and after infiltration with PDMS, the resist was removed in a water-based basic solution which avoided PDMS swelling or pattern collapse occurring during the ILT removal process. Since the period of the structure is approximately 1 microm, the density of states of gigahertz phonons are altered by the phononic PDMS/air crystal. Brillouin light scattering (BLS) was employed to measure phononic modes of the structure as a function of mechanical strain. The results demonstrate that the phononic band diagram of such structures can be tuned mechanically.

Air↗
PubMed2006

Optically pumped surface-emitting lasing using self-assembled block-copolymer-distributed Bragg reflectors.

A thin-film organic laser cavity using a block-copolymer-based one-dimensional (1D) photonic crystal was fabricated. Polymeric distributed Bragg reflectors (DBRs) were prepared through the self-assembly of a lamellar-forming poly(styrene-b-isoprene) (PS-b-PI) diblock copolymer having a 1D photonic stop band overlapping with the fluorescence spectrum of a gain medium. Optically pumped surface-emitting lasing was obtained using poly(methyl methacrylate) (PMMA) doped with 1,4-di-(2-methylstyryl)benzene (Bis-MSB) as an organic gain medium and the polymeric self-assembled DBR as a spectral-band selective feedback element.

Crystallization↗
PubMed2006

Electrospun polymer nanofibers with internal periodic structure obtained by microphase separation of cylindrically confined block copolymers.

Continuous fibers are described having concentric layer or aligned sphere microphase-separated, styrene-isoprene block copolymer morphologies. The fibers are obtained by a two-fluid coaxial electrospinning technique in which the desired block copolymer is encapsulated as the core component within a polymer shell having a high glass transition temperature (Tg). The fibers range in diameter from 300 to 800 nm, and the block copolymer core ranges from 50 to 500 nm. Subsequent annealing of the fibers above the upper Tg of the block copolymer but below the Tg of the shell polymer results in microphase separation of the block copolymer under cylindrical confinement. The resulting fibers exhibit improved long-range order. This two-step strategy creates the opportunity to fabricate continuous nanofibers with periodic internal structure.

Journal Article↗
PubMed2005

perpendicular organization of macromolecules: synthesis and alignment studies of a soluble poly(iptycene).

We describe herein a polymeric material that prefers to align perpendicular to a stretch-aligned polymer host in the solid state. Poly(iptycene) poly-1 was synthesized from monomer 1 under hyperbaric techniques via a Diels-Alder polymerization. Polarized excitation spectra of the anthracene end groups in this material in a stretch-aligned, solution-cast poly(vinyl chloride) (PVC) film showed that the poly(iptycene) prefers to align normal (counter aspect ratio) to the stretching direction of the PVC. This is explained by a "threading" mechanism, whereby the PVC intercalates through the internal free volume presented by poly-1, similar to effects observed in small molecule iptycenes under similar conditions.

Journal Article↗
PubMed2005

2D spatially periodic architectures via the drying of 1D holographically photopatterned polymer solutions.

We demonstrate an efficient and versatile method for selectively generating 1D and 2D periodic polymer structures in the submicron to tens of micron range by the directed drying of 1D photopatterned polymer solutions. Ultraviolet (UV) holographic lithography (Xia et al. Chem. Rev. 1999, 99, 1823-1848) is initially used to create 1D periodic cross-link and density variations in the polymer/volatile solvent solutions. These variations act as anisotropic barriers (walls) that direct the subsequent solvent evaporation process. Somewhat akin to directional drying (Allain and Limat Phys. Rev. Lett. 1995, 74, 2981-2984) and directional solidification (Pelc, P. Dynamics of Curved Fronts; Academic Press: San Diego, CA, 1988) experiments, the drying exhibits channel-like interface propagation behavior. The combination of the instabilities and minimization of the interface area during drying can be effectively used to produce larger scale 2D pseudohexagonal polymer-strut structures, or by the addition of a monomeric component to the polymer solution, the instabilities can be suppressed, resulting in the formation of 1D linear gratings.

Journal Article↗
PubMed2004

Proximity effects in self-organized binary particle-block copolymer blends.

Dependent on the surface chemistry of gold nanocrystals of equal metal core size, two morphological types of self-organized block copolymer-particle blends are observed: (1) the segregation of the nanocrystals to the interfacial areas or (2) the preferential uniform distribution within one of the respective polymer domains. The confinement of the nanocrystals to the narrow interfacial regions of the microstructure in type one blends results in high local particle filling fractions and gives rise to electromagnetic coupling upon light irradiation, accompanied by a pronounced increase in absorbance.

Journal Article↗
PubMed2004

Onset of tethered chain overcrowding.

We proposed an approach to precisely control the density of tethered chains on solid substrates using PEO-b-PS and PLLA-b-PS. As the crystallization temperature Tx increased, the PEO or PLLA lamellar crystal thickness d(L) increased as well as the reduced tethering density sigma; of the PS chains. The onset of tethered PS chains overcrowding in solution occurs at sigma(*) approximately 3.7-3.8 as evidenced by an abrupt change in the slope between (d(L))(-1) and Tx. This results from the extra surface free energy created by the tethered chain that starts to affect the growth barrier of the crystalline blocks.

Journal Article↗
PubMed2004

Diamond-structured photonic crystals.

Certain periodic dielectric structures can prohibit the propagation of light for all directions within a frequency range. These 'photonic crystals' allow researchers to modify the interaction between electromagnetic fields and dielectric media from radio to optical wavelengths. Their technological potential, such as the inhibition of spontaneous emission, enhancement of semiconductor lasers, and integration and miniaturization of optical components, makes the search for an easy-to-craft photonic crystal with a large bandgap a major field of study. This progress article surveys a collection of robust complete three-dimensional dielectric photonic-bandgap structures for the visible and near-infrared regimes based on the diamond morphology together with their specific fabrication techniques. The basic origin of the complete photonic bandgap for the 'champion' diamond morphology is described in terms of dielectric modulations along principal directions. Progress in three-dimensional interference lithography for fabrication of near-champion diamond-based structures is also discussed.

Crystallization↗
PubMed2003

Exploring for 3D photonic bandgap structures in the 11 f.c.c. space groups.

The promise of photonic crystals and their potential applications has attracted considerable attention towards the establishment of periodic dielectric structures that in addition to possessing robust complete bandgaps, can be easily fabricated with current techniques. A number of theoretical structures have been proposed. To date, the best complete photonic bandgap structure is that of diamond networks having Fd3m symmetry (2-3 gap). The only other known complete bandgap in a face-centred-cubic (f.c.c.) lattice structure is that of air spheres in a dielectric matrix (8-9 gap; the so called 'inverse-opal' structure). Importantly, there is no systematic approach to discovering champion photonic crystal structures. Here we propose a level-set approach based on crystallography to systematically examine for photonic bandgap structures and illustrate this approach by applying it to the 11 f.c.c. groups. This approach gives us an insight into the effects of symmetry and connectivity. We classify the F-space groups into four fundamental geometries on the basis of the connectivity of high-symmetry Wyckoff sites. Three of the fundamental geometries studied display complete bandgaps--including two: the F-RD structure with Fm3m symmetry and a group 216 structure with F43m symmetry that have not been reported previously. By using this systematic approach we were able to open gaps between the 2-3, 5-6 and 8-9 bands in the f.c.c. systems.

Journal Article↗
PubMed2003

Polarized photoluminescence from poly(p-phenylene-ethynylene) via a block copolymer nanotemplate.

A new approach based on a conjugated polymer/block copolymer guest/host system for the generation of polarized photoluminescence is reported. Synthetic modification of a poly(p-phenylene-ethynylene) (PPE) conjugated polymer is used for domain-specific incorporation into a cylindrical morphology block copolymer host matrix. Subsequent ordering of the host nanostructure via roll cast processing templates uniaxial alignment of the guest PPE. The ordered films are optically anisotropic displaying both polarized absorption with a dichroic ratio of 3.0 at 440 nm and polarized emission with a polarization ratio of 7.3 at 472 nm.

Journal Article↗
PubMed2003

Fourier analysis near-field polarimetry for measurement of local optical properties of thin films.

We present measurements of the local diattenuation and retardance of thin-film specimens by using techniques that combine near-field scanning optical microscopy (NSOM) and a novel polarization-modulation (PM) polarimetry utilizing Fourier analysis of the detected intensity signal. Generally, quantitative near-field polarimetry is hampered by the optical anisotropy of NSOM probes. For example, widely used aluminum-coated pulled-fiber aperture probes typically exhibit a diattenuation near 10%. Our analysis of aperture diattenuation demonstrates that the usual techniques for nulling a PM polarimeter result in a nonzero residual probe retardance in the presence of a diattenuating tip. However, we show that both diattenuation and retardance of the sample can be determined if the corresponding tip properties are explicitly measured and accounted for in the data. In addition, in thin films (<100 nm thick), where the sample retardance and diattenuation are often small, we show how to determine these polarimetric quantities without requiring alignment of the fast and diattenuating axes, which is a more general case than has been previously discussed. We demonstrate our techniques by using two types of polymer-film specimens: ultrahigh molecular weight block copolymers (recently noted for their photonic activity) and isotactic polystyrene spherulites. Finally, we discuss how changes in the tip diattenuation during data collection can limit the accuracy of near-field polarimetry and what steps can be taken to improve these techniques.

Journal Article↗
PubMed2003

Size-selective organization of enthalpic compatibilized nanocrystals in ternary block copolymer/particle mixtures.

Dependent on the relative particle core size, two distinct types of particle topologies in block copolymer/nanocrystal blends have been identified, that is, the localization of particles along the intermaterial dividing surface or at the center of the respective polymer domain. In ternary systems consisting of block copolymer and two different-sized nanocrystal species, the distinct morphological types are conserved, resulting in autonomous size-selective separation and organization of the respective nanocrystals within alternating arrays and sheets.

Journal Article↗
PubMed2003

Acoustic excitations in a self-assembled block copolymer photonic crystal.

High resolution Brillouin light scattering can sensitively detect acoustic phonons in concentrated solutions of a high molecular weight poly(styrene-b-isoprene) symmetric copolymer in toluene. This block copolymer lamellar forming system also possesses a photonic stop band in the visible spectrum. Based on the low but finite contrast in mechanical properties between the styrene and isoprene components and taking into account the geometrical characteristics of the layered microstructure, we calculate the acoustic band structure and represent the observed acousticlike and opticlike phonons.

Journal Article↗
PubMed2003

Triply periodic bicontinuous structures through interference lithography: a level-set approach.

Interference lithography holds the promise of fabricating large-area, defect-free photonic structures on the sub-micrometer scale both rapidly and cheaply. There is a need for a procedure to establish a connection between the structures that are formed and the parameters of the interfering beams. There is also a need to produce self-supporting three-dimensional bicontinuous structures. A generic technique correlating parameters of the interfering beams with the symmetry elements present in the resultant structures by a level-set approach is developed. A particular space group is ensured by equating terms of the intensity equation to a representative level surface of the desired space group. Single- and multiple-exposure techniques are discussed. The beam parameters for certain cubic bicontinuous structures relevant to photonic crystals, viz.,the diamond(D), the simple cubic (P), and the chiral gyroid (G) are derived by utilizing either linear or elliptically polarized light.

Journal Article↗
PubMed2002

Site-isolated luminescent europium complexes with polyester macroligands: metal-centered heteroarm stars and nanoscale assemblies with labile block junctions.

The synthesis of a series of polymeric Eu(III) complexes with polyester ligands, along with supporting emission spectra, luminescence lifetimes, and, for a Eu block copolymer film, atomic force microscopy (AFM) data, is presented. Dibenzoylmethane was derivatized with a hydroxyl initiator site (dbmOH, 1) for tin octoate catalyzed ring opening polymerization of dl-lactide. The resulting poly(lactic acid) macroligand, dbmPLA (2), was combined with EuCl3 to generate Eu(dbmPLA)3 (3). Chelation of both dbmPLA and a polycaprolactone-functionalized bipyridine ligand (bpyPCL2) led to the Eu(III)-centered heteroarm star Eu(dbmPLA)3(bpyPCL2) (4). Unpolarized emission spectra and luminescence lifetimes were recorded for the Eu polymers in CH2Cl2 and for Eu(dbmPLA)3, as a film. Solution data for Eu(dbm)3 and Eu(dbm)3(bpy) were collected for comparison. For Eu tris(dbm) complexes, data were fit to a double exponential decay, indicating the presence of multiple species. Relative amounts of the longer lifetime component increase in the series Eu(dbm)3 solutions to Eu(dbmPLA)3 solutions to Eu(dbmPLA)3 films, perhaps suggesting benefits of the "polymer shell effect" and the diminishment of aquo adducts known to shorten lifetimes. As with the nonpolymeric analogue, data for Eu(dbmPLA)3(bpyPCL2) fit to a single-exponential decay. The sharpness of the feature at 579.7 nm, attributable to the 5D0 --> 7F0 transition in the emission spectrum of 4, lends further support for a homogeneous sample. AFM studies of "as cast" thin films of 4 reveal a lamellar structure with a 17.5 nm repeat. These microstructures, inferred to contain Eu luminophores at the glassy PLA-crystalline PCL domain interfaces, are modified by thermal treatment.

2,2'-Dipyridyl↗
PubMed2002

A surface-reactive rod-coil diblock copolymer: nano- and micropatterned polymer brushes.

A diblock copolymer consisting of poly(3-(triethoxysilyl)propylisocyanate) (PIC) and polystyrene(PS) was synthesized by anionic polymerization. A polymeric monolayer of the block copolymer was formed on silica substrates by various grafting techniques such as immersion, casting, or contact-printing. The PIC block adheres covalently to Si substrates in an in-plane fashion due to its extended rodlike conformation and reactivity to the silica. The polystyrene blocks aggregate to form mounds on the surface resulting in a new type of nanopatterned polymer brush. The self-limiting adsorption of the rod coils results in a thickness of about 5 nm regardless of the solution concentration and coating method. This particular property allowed microcontact printing directly onto silicon or glass substrates. The resulting surface morphology consisted of nanoscale domains given by the block copolymer and uniform thickness micropatterns transferred from the stamp within the printed area. This study offers a simple new method to prepare a covalent polymeric monolayer with nano- and micropatterns, which can be performed directly onto various silicon-based substrates.

Isocyanates↗