Gold gyroid optical metamaterials are known to possess a reduced plasma frequency and linear dichroism imparted by their intricate subwavelength single gyroid morphology. The anisotropic optical properties are, however, only evident when a large individual gyroid domain is investigated. Multidomain gyroid metamaterials, fabricated using a polyisoprene--polystyrene--poly(ethylene oxide) triblock terpolymer and consisting of multiple small gyroid domains with random orientation and handedness, instead exhibit isotropic optical properties. Comparing three effective medium models, we here show that the specular reflectance spectra of such multidomain gyroid optical metamaterials can be accurately modeled over a broad range of incident angles by a Bruggeman effective medium consisting of a random wire array. This model accurately reproduces previously published results tracking the variation in normal incidence reflectance spectra of gold gyroid optical metamaterials as a function of host refractive index and volume fill fraction of gold. The effective permittivity derived from this theory confirms the change in sign of the real part of the permittivity in the visible spectral region (so, that gold gyroid metamaterials exhibit both dielectric and metallic behavior at optical wavelengths). That a Bruggeman effective medium can accurately model the experimental reflectance spectra implies that small multidomain gold gyroid optical metamaterials behave both qualitatively and quantitatively as an amorphous composite of gold and air (i.e., nanoporous gold) and that coherent electromagnetic contributions arising from the subwavelength gyroid symmetry are not dominant.
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http://dx.doi.org/10.1021/acsphotonics.6b00400 | DOI Listing |
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October 2024
Soft Hybrid Materials Research Center, Korea Institute of Science and Technology, Seoul, 02792, Republic of Korea.
The gyroid structure from self-assembly is highly attractive for optical applications such as photonic crystals and metamaterials. However, due to the direction-dependent nature of these applications, achieving a monograin-level structure over a large area has remained challenging. In this study, the fabrication of unidirectionally oriented anisotropic nanocylinders of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) is reported block copolymer thin films up to a 4-inch scale via a shear-rolling process, followed by solvent annealing to induce phase transition to nearly monograin gyroid structures.
View Article and Find Full Text PDFJ R Soc Interface
September 2024
Department of Chemistry and Physics of Materials, University of Salzburg, Salzburg 5020, Austria.
Biophotonic nanostructures in butterfly wing scales remain fascinating examples of biological functional materials, with intriguing open questions with regard to formation and evolutionary function. One particularly interesting butterfly species, (Lycaenidae: Theclinae), develops wing scales that contain three-dimensional photonic crystals that closely resemble a single gyroid geometry. Unlike most other gyroid-forming butterflies, develops discrete gyroid crystallites with a pronounced size gradient hinting at a developmental sequence frozen in time.
View Article and Find Full Text PDFJ Chem Phys
August 2024
Department of Chemical Engineering and Materials Science, University of Minnesota - Twin Cities, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, USA.
Thin-film confinement of self-assembling block polymers results in materials with myriad potential applications-including membranes and optical devices-and provides design parameters for altering phase behavior that are not available in the bulk, namely, film thickness and preferential wetting. However, most research has been limited to lamella- and cylinder-forming polymers; three-dimensional phases, such as double gyroid (DG), have been observed in thin films, but their phase behavior under confinement is not yet well understood. We use self-consistent field theory to predict the equilibrium morphology of bulk-gyroid-forming AB diblock polymers under thin-film confinement.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2024
Department of Chemistry, Indian Institute of Science Education and Research Pune, Dr. Homi Bhabha Road, Pune 411008, India.
Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CHCHCH(CH)NH][CHCHCH(CH)NH][PF] () crystallizing in the polar monoclinic 2 space group. The asymmetry in was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF anion and the consequent formation of salt cocrystal.
View Article and Find Full Text PDFJ Phys Chem A
March 2024
Faculty of Chemistry, Physicochemistry of Carbon Materials Research Group, Nicolaus Copernicus University in Toruń, 87-100 Toruń, Poland.
Triply periodic minimal surfaces (TPMS) inspired by nature serve as a foundation for developing novel nanomaterials, such as templated silicas, graphene sponges, and schwarzites, with customizable optical, poroelastic, adsorptive, catalytic, and other properties. Computer simulations of reactions on TPMS using reactive intermolecular potentials hold great promise for constructing and screening potential TPMS with the desired properties. Here, we developed an off-lattice, surface-constrained Metropolis Monte Carlo (SC-MMC) algorithm that utilized a temperature quench process.
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