Advances in determination of polymer structure and in preservation of structure for electron microscopy provide the best view to date of how polysaccharides and structural proteins are organized into plant cell walls. The walls that form and partition dividing cells are modified chemically and structurally from the walls expanding to provide a cell with its functional form. In grasses, the chemical structure of the wall differs from that of all other flowering plant species that have been examined. Nevertheless, both types of wall must conform to the same physical laws. Cell expansion occurs via strictly regulated reorientation of each of the wall's components that first permits the wall to stretch in specific directions and then lock into final shape. This review integrates information on the chemical structure of individual polymers with data obtained from new techniques used to probe the arrangement of the polymers within the walls of individual cells. We provide structural models of two distinct types of walls in flowering plants consistent with the physical properties of the wall and its components.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1365-313X.1993.tb00007.x

Structural models of primary cell walls in flowering plants: consistency of molecular structure with the physical properties of the walls during growth

Metamaterials, or engineered materials with rationally designed, subwavelength-scale building blocks, allow us to control the behavior of physical fields in optical, microwave, radio, acoustic, heat transfer, and other applications with flexibility and performance that are unattainable with naturally available materials. In turn, metasurfaces-planar, ultrathin metamaterials-extend these capabilities even further. Optical metasurfaces offer the fascinating possibility of controlling light with surface-confined, flat components. In the planar photonics concept, it is the reduced dimensionality of the optical metasurfaces that enables new physics and, therefore, leads to functionalities and applications that are distinctly different from those achievable with bulk, multilayer metamaterials. Here, we review the progress in developing optical metasurfaces that has occurred over the past few years with an eye toward the promising future directions in the field.

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Planar Photonics with Metasurfaces

Optical generation of hot electrons in metallic structures and its potential as an alternative to conventional electron–hole separation in semiconductor devices are reviewed. The possibilities for realizing high conversion efficiencies with low fabrication costs are discussed along with challenges in terms of the materials, architectures and fabrication methods

Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices

Materials research plays a vital role in transforming breakthrough scientific ideas into next-generation technology. Similar to the way silicon revolutionized the microelectronics industry, the proper materials can greatly impact the field of plasmonics and metamaterials. Currently, research in plasmonics and metamaterials lacks good material building blocks in order to realize useful devices. Such devices suffer from many drawbacks arising from the undesirable properties of their material building blocks, especially metals. There are many materials, other than conventional metallic components such as gold and silver, that exhibit metallic properties and provide advantages in device performance, design flexibility, fabrication, integration, and tunability. This review explores different material classes for plasmonic and metamaterial applications, such as conventional semiconductors, transparent conducting oxides, perovskite oxides, metal nitrides, silicides, germanides, and 2D materials such as graphene. This review provides a summary of the recent developments in the search for better plasmonic materials and an outlook of further research directions.

/pdf/alternative-plasmonic-materials-beyond-gold-and-silver-1p8fd7ol50.pdf

Alternative Plasmonic Materials: Beyond Gold and Silver

Pectins: structure, biosynthesis, and oligogalacturonide-related signaling.

As alternatives to conventional metals, new plasmonic materials offer many advantages in the rapidly growing fields of plasmonics and metamaterials. These advantages include low intrinsic loss, semiconductor-based design, compatibility with standard nanofabrication processes, tunability, and others. Transparent conducting oxides such as Al:ZnO, Ga:ZnO and indium-tin-oxide (ITO) enable many high-performance metamaterial devices operating in the near-IR. Transition-metal nitrides such as TiN or ZrN can be substitutes for conventional metals in the visible frequencies. In this paper we provide the details of fabrication and characterization of these new materials and discuss their suitability for a number of metamaterial and plasmonic applications.

/pdf/oxides-and-nitrides-as-alternative-plasmonic-materials-in-3m2s4np5d2.pdf

Oxides and nitrides as alternative plasmonic materials in the optical range [Invited]

Cell walls of grasses have two major polysaccharides that contain uronic acids, the hemicellulosic glucuronoarabinoxylans and the galactosyluronic acid-rich pectins. A technique whereby esterified uronic acid carboxyl groups are reduced selectively to yield their respective 6,6-dideuterio neutral sugars was used to determine the extent of esterification and changes in esterification of these two uronic acids during elongation of maize (Zea mays L.) coleoptiles. The glucosyluronic acids of glucuronoarabinoxylans did not appear to be esterified at any time during coleoptile elongation. The galactosyluronic acids of embryonal coleoptiles were about 65% esterified, but this proportion increased to nearly 80% during the rapid elongation phase before returning to about 60% at the end of elongation. Methyl esters accounted for about two-thirds of the total esterified galacturonic acid in cell walls of unexpanded coleoptiles. The proportion of methyl esters decreased throughout elongation and did not account for the increase in the proportion of esterified galactosyluronic acid units during growth. The results indicate that the galactosyluronic acid units of grass pectic polysaccharides may be converted to other kinds of esters or form ester-like chemical interactions during expansion of the cell wall. Accumulation of novel esters or ester-like interactions is coincident with covalent attachment of polymers containing galactosyluronic acid units to the cell wall.

Changes in Esterification of the Uronic Acid Groups of Cell Wall Polysaccharides during Elongation of Maize Coleoptiles

Transparent conducting oxides have recently gained great attention as CMOS-compatible materials for applications in nanophotonics due to their low optical loss, metal-like behavior, versatile/tailorable optical properties, and established fabrication procedures. In particular, aluminum-doped zinc oxide (AZO) is very attractive because its dielectric permittivity can be engineered over a broad range in the near-IR and IR. However, despite all these beneficial features, the slow (>100  ps) electron-hole recombination time typical of these compounds still represents a fundamental limitation impeding ultrafast optical modulation. Here we report the first epsilon-near-zero AZO thin films that simultaneously exhibit ultrafast carrier dynamics (excitation and recombination time below 1 ps) and an outstanding reflectance modulation up to 40% for very low pump fluence levels (<4  mJ/cm2) at a telecom wavelength of 1.3 μm. The unique properties of the demonstrated AZO thin films are the result of a low-temperature fabrication procedure promoting deep-level defects within the film and an ultrahigh carrier concentration.

Epsilon-near-zero Al-doped ZnO for ultrafast switching at telecom wavelengths

Radiation patterns and the resonance wavelength of a plasmonic antenna are significantly influenced by its local environment, particularly its substrate. Here, we experimentally explore the role of dispersive substrates, such as aluminum- or gallium-doped zinc oxide in the near infrared and 4H-silicon carbide in the mid-infrared, upon Au plasmonic antennas, extending from dielectric to metal-like regimes, crossing through epsilon-near-zero (ENZ) conditions. We demonstrate that the vanishing index of refraction within this transition induces a “slowing down” of the rate of spectral shift for the antenna resonance frequency, resulting in an eventual “pinning” of the resonance near the ENZ frequency. This condition corresponds to a strong backward emission with near-constant phase. By comparing heavily doped semiconductors and undoped, polar dielectric substrates with ENZ conditions in the near- and mid-infrared, respectively, we also demonstrate the generality of the phenomenon using both surface plasmon and phonon polaritons, respectively. Furthermore, we also show that the redirected antenna radiation induces a Fano-like interference and an apparent stimulation of optic phonons within SiC.

Role of epsilon-near-zero substrates in the optical response of plasmonic antennas

Transparent conducting oxides (TCOs) are emerging as possible alternative constituent materials to replace noble metals such as silver and gold for low-loss plasmonic and metamaterial (MM) applications in the near infrared regime (NIR). The optical characteristics of TCOs have been studied to evaluate the functionalities and potential of these materials as metal substitutes in plasmonic and MM devices, even apart from their usual use as electrode materials. However, patterning TCOs at the nanoscale, which is necessary for plasmonic and MM devices, is not well studied. This paper investigates nanopatterning processes for TCOs, especially the liftoff technique with electron-beam lithography, and the realization of plasmonic nanostructures with TCOs. By employing the developed nanopatterning process, we fabricate 2-D-periodic arrays of TCO nanodisks and characterize the material's plasmonic properties to evaluate the performance of TCOs as metal substitutes. Light-induced collective oscillations of the free electrons in the TCOs (bulk plasmons) and localized surface plasmon resonances are observed in the wavelength range from 1.6 to 2.1 μm. Well-defined resonance peaks are observed, which can be dramatically tuned by varying the amount of dopant and by thermally annealing the TCO nanodisks in nitrogen gas ambient while maintaining the low-loss properties.

Jongbum Kim

Papers

Oxides and nitrides as alternative plasmonic materials in the optical range [Invited]

Changes in Esterification of the Uronic Acid Groups of Cell Wall Polysaccharides during Elongation of Maize Coleoptiles

Epsilon-near-zero Al-doped ZnO for ultrafast switching at telecom wavelengths

Role of epsilon-near-zero substrates in the optical response of plasmonic antennas

Plasmonic Resonances in Nanostructured Transparent Conducting Oxide Films