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Various compositions of Li1-2xCaxSi2N3 (x = 0–0.2) were synthesized by the reaction of Li3N, Si3N4, and Ca3N2 at temperatures of 1873–2073 K. Ca was incorporated into the LiSi2N3 host lattice to form a solid solution of Li1-2xCaxSi2N3. The activation energy for ionic conduction was decreased and ionic conductivity at room temperature was enhanced by Ca doping. At 298 K, the ionic conductivity of densified Li1-2xCaxSi2N3 (x = 0.075) ceramic reached 1.6 × 10−5 S m−1, almost four orders of magnitude higher than that of densified Li1-2xCaxSi2N3 (x = 0) ceramic (3.1 × 10−9 S m−1). The change in the LiSi2N3 framework upon Ca doping decreased the interaction between the ions and increased the number of defects in the structure, making it easier for mobile Li+ ions to migrate. Moreover, the incorporation of aliovalent substitutional Ca2+ ions in the LiSi2N3 lattice is expected to create Li+ vacancies (VLi) for charge compensation (Li1-2xCaxVLiSi2N3), thereby increasing the number of mobile Li+ ions.
Hierarchical ZnO/Si nanoheterostructure was prepared by growing oriented ZnO nanowire bundles onto the top of nanoporous silicon pillar array (NSPA) via a self-catalytic thermal evaporation and vapor-phase transport method. Samples were carefully characterized using field emission scanning electron microscopy, x-ray diffraction, and luminescence spectroscopy. One ultraviolet, one blue-green, and two red emission bands were observed in ZnO/NSPA, and the emission mechanism is discussed by developing a model-based energy band diagram. The origins of the ultraviolet and blue-green photoluminescence (PL) bands were attributed to the emission from the band edge transition and surface states of oxygen vacancies of ZnO, while two red PL bands originated from NSPA and could be well explained by the quantum confinement-luminescence center model. The realization of such all solid and wide wavelength nanodevice might be both meaningful for developing new concept lighting devices and potentially extended to fabricate hierarchical Si-based nanoheterostructures in fabricating other optoelectronic nanodevices.
By measuring the ion concentration in a pressure-induced infiltration experiment on a hydrophobic Zeolite Socony Mobil-5, it is found that the nanopore wall has a strong ion repelling effect. When the initial ion concentration is relatively low, only water molecules can enter the nanopores. Once the initial ion concentration is relatively high, ions can infiltrate into the nanopores, but the effective ion concentration of the confined liquid is much lower.
The thermal transitions and the nonisothermal cold crystallization kinetics of poly(ethylene terephthalate) (PET) at constant heating rates were investigated using differential scanning calorimetry. It was found that the glass transition and crystallization temperature increased with the heating rates, while the melting temperature showed a little variation for the heating rates used. Crystallization and melting latent heats were remarkably constant, independent of the heating rate. Kinetics parameters were determined using Ozawa model. Two different kinetic regimes were identified, corresponding to primary and secondary crystallization, at low and high fractional crystallization, respectively, both following Ozawa’s model. Kinetics parameters were determined for the primary and secondary regimes; the pre-exponential constant (KT) and Ozawa’s exponent (m) decreased with increasing crystallization temperature. The combined kinetic parameter increased exponentially with temperature; activation energies were estimated using Arrhenius plots for the two PET crystallization regimes.
A facile ethylene glycol–based solvothermal method was developed for the synthesis of lanthanide orthovanadate LnVO4 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu) nanoparticles with relatively uniform size and morphologies. The LnVO4 nanoparticles ranged from 100 to 500 nm and changed from spheres to ellipses and platelet–shaped particles depending on the ionic size. Radius of the Ln ions affected crystal structure. The particles with larger ions form monoclinic-type structure for LaVO4 and with smaller ions form zircon-type structure for LnVO4 (Ln = Pr-Yb). A nucleation and aggregates formation mechanism of LnVO4 nanomaterials was proposed to illustrate the crystal growth. The morphologies of LnVO4 nanoparticles could be turned by pH value and molar ratio of reactants. Spherical LaVO4 and PrVO4 nanoparticles were obtained at pH 6, whereas elliptical nanoparticles were obtained at pH 3. Eu3+-, Dy3+-, and Sm3+-doped zircon-type YVO4 nanoparticles exhibit strong luminescence typical of doped ions.
By
A. A. Maradudin, University of California, Irvine, CA 92697 USA,
E. R. Méndez, División de Física Aplicada, Centro de Investigación Científica y de Educación Superior de Ensenada, Carretera Ensenada-Tijuana No. 3918, Ensenada, B. C., 22860, México,
T. A. Leskova, University of California, Irvine, CA 92697 USA
A reader of this book will quickly see that structured surfaces, whether deterministic or random, can reflect, transmit, refract, and amplify volume or surface electromagnetic waves in ways that naturally occurring surfaces cannot. They can also change the nature of an electromagnetic field incident on them. For example, they can change a beam with one intensity distribution into a beam with a different intensity distribution, or they can convert a plane wave into a beam. The use of structured surfaces, specifically randomly rough surfaces, to effect such transformations of optical fields is the subject of this chapter, where two examples of this use are presented, namely beam shaping and the formation of pseudo-nondiffracting beams.
The creation of optical elements that transform an electromagnetic beam with a specified transverse intensity distribution into a beam with a different specified transverse intensity distribution, especially those that transform a laser beam with a Gaussian intensity profile into a beam with a constant intensity profile – a flat top beam, has been studied theoretically and experimentally for many years [1–38]. The interest in beam shaping is due to a wide range of applications for beams with a variety of non-Gaussian intensity distributions. These applications include laser surgery [39], laser radar [40], laser microstructuring of materials [41], metal hardening [42], optical communication [43], and optical scanning [44], among others. Some of them and other applications of beam shaping are discussed in the recent book by Dickey et al. [45].
The structuring of a metal at nanoscale dimensions results in novel optical properties that are not present for bulk metals. Metallic photonic crystals, metal-based structures with periodicities on the scale of the wavelength of light, have attracted particular attention due to their unique optical properties. Among the approaches taken to prepare a three-dimensional photonic crystal is to take advantage of the self-assembly of spheres from a colloidal solution. Spherical colloidal particles of polymers or silica with diameters ranging from 20 nm up to 1 μm and larger, with low coefficients of variation in their diameter, are readily available. The methods of producing monodispersive colloids are well discussed in ref. [1]. The importance and interest of these particles lies in the fact that it is possible to induce them into a close-packed structure analogous to an ordinary close-packed crystal. There are several methods for self-assembly of colloidal spheres, in particular, sedimentation, evaporation, and electrophoresis. These close-packed arrays of uniform particles offer an attractive and, in principle, simple means to template the three-dimensional structure of a variety of materials.
Generally, self-assembly is restricted to the formation of close-packed two-dimensional or three-dimensional assemblies of colloidal particles. However, the low cost and availability of a relatively easy protocol to obtain this type of photonic crystals, artificial opals, make the self-assembly technique very attractive and widely used. The next step in the development of this technique to prepare metallic photonic crystal is to infiltrate the sample with some appropriate material, removing the original structure, and obtaining in this way inverted opals.
Surface plasmon polariton (SPP) modes have attracted much interest in recent years. Although known and studied for over 100 years [1–3], the dream of confining light to dimensions smaller than its propagating wavelength has led the way towards technological possibilities not previously addressed, such as optical circuitry within ultra small computer processors [4, 5], or small biochemical sensors [6, 7]. Confinement of light to sub-wavelength dimensions is also a possibility when one considers the field aspects of the electromagnetic waves near surfaces (near-field phenomena). Add to this the interest in materials and structures exhibiting a negative refractive index for the purpose of increasing the resolution of optical microscopy [8], and it is no wonder that the area of electromagnetic (EM) propagation in sub-wavelength structures is enjoying a renewed interest. Whether the far-field aspects of periodic resonating metallo-dielectric structures are the true manifestations of a negative refractive index or simply a unique, but already known, near-field dispersion phenomenon may be debated [9]. Nonetheless, the near-field aspects of periodic sub-wavelength metallo-dielectric structures, and especially recent advances in nano-fabrication of structures at dimensions smaller than optical wavelengths, deserve a closer look.
Artificial dielectrics (ADs) constitute a class of man-made materials: the effective permittivity and permeability of a given dielectric material may be altered by imbedding metallic or semiconductive structures on scales smaller than the propagating wavelength. For example, one may alter the equivalent capacitance and inductance of microwave waveguides by the addition of a pattern of fine metallic features along the waveguide axis.
By
F. M. Izrailev, Universidad Autónoma de Puebla, Apdo. Post. J-48, Puebla 72570, México,
N. M. Makarov, Universidad Autónoma de Puebla, Priv. 17 Norte No. 3417, Col. San Miguel Hueyotlipan, Puebla 72050, México
In recent years, increasing attention has been paid to the so-called correlated disorder in low-dimensional disordered systems. Interest in this subject is mainly due to two reasons. First, it was found that specific correlations in a disordered potential can result in quite unexpected anomalous properties of scattering. Second, it was shown that such correlations can be relatively easily constructed experimentally, at least in the one-dimensional Anderson model and in Kronig–Penney models of various types. Therefore, it seems to be feasible to fabricate random structures with desired scattering properties, in particular when one needs to suppress or enhance the localization in given frequency windows for scattering electrons or electromagnetic waves. In addition, it was understood that, in many real systems, correlated disorder is an intrinsic property of the underlying structures. One of the most important examples is a DNA chain, for which strong correlations in the potential have been shown to manifest themselves in an anomalous conductance. Thus, the subject of correlated disorder is important both from the theoretical viewpoint, and for various applications in physics.
The key point of the theory of correlated disorder is that the localization length for eigenstates in one-dimensional models absorbs the main effect of correlations in disordered potentials. This fact has been known since the earliest analytical studies of transport in continuous random potentials. However, until recently the main interest was in delta-correlated potentials, or in potentials with a Gaussian-type of correlation.
Cloaking is the ability to make a region of space, and everything in it, invisible to an external observer. It has been the dream of fantasy writers for decades. In 2009, John Mullan [1] of The Guardian newspaper summarized the ten most important works that use the theme: The Invisible Man by H. G. Wells, The Republic by Plato, The Lord of the Rings by J. R. R. Tolkien, the Harry Potter books by J. K. Rowling, Theogony by Hesiod, Dr Faustus by Christopher Marlowe, The Tempest by William Shakespeare, The Voyage of the Dawn Treader by C. S. Lewis, The Emperor's New Clothes by Hans Christian Andersen, and The Hitchhiker's Guide to the Galaxy by Douglas Adams. A true cloak allows the clear observation of the space behind the cloaked region, and the cloaked region casts no shadow and produces no wavefront changes in the light that has passed through the cloaked region. It is not possible to build a perfect invisibility cloak, as was perceptively observed in the Star Trek series in which cloaked Romulan and Klingon spaceships could be detected by the subtle disturbances of space that the cloak produced.
Interest in making real cloaking devices can be traced to two seminal articles, one by John Pendry and his co-workers [2], and the other by Ulf Leonhardt [3]. Their approach can be called the transformational optics approach to cloaking, which will be discussed in more detail later.
By
Evgeny Popov, Aix-Marseille Université, CNRS, Unité Mixte de Recherche 6133, Domaine Universitaire de Saint Jerome, 13397 Marseille Cedex 20, France,
Nicolas Bonod, Aix-Marseille Université, CNRS, Unité Mixte de Recherche 6133, Domaine Universitaire de Saint Jerome, 13397 Marseille Cedex 20, France
A brief reminder of the history of grating anomalies and plasmon surface waves
The recent history of the research and development around plasmon surface waves that was initiated by the work published in Nature in 1998 by Ebbesen et al. [1] looks like a ten-fold compressed version of studies initiated more than a century ago by Robert Wood with his discovery of anomalies in the efficiency of metallic diffraction gratings, now known as Wood's anomalies [2]. In 1902, R. Wood wrote: “I was astounded to find that under certain conditions, the drop from maximum illumination to minimum, a drop certainly from 10 to 1, occurred within a range of wavelengths not greater than the distance between the sodium lines,” an observation that marked the discovery of grating anomalies.
The first period of the search for their explanation is marked by the attempt of Lord Rayleigh [3, 4] to link Wood's anomalies to the redistribution of the energy due to the passing-off (cut-off) of higher diffraction orders of the grating (transfer from propagating into evanescent type). As pointed out by Maystre [5], his prediction was all the more remarkable as the author first ignored the groove frequency of the grating used by Wood, and thus could not verify this assumption with experimental data.
In recent years it has emerged that planar metamaterials offer a vast range of custom-designed electromagnetic functionalities. The best known are wire grid polarizers, which are established standard components for microwaves, terahertz waves, and the far-infrared. They are expected to be of increasing importance also for the near-infrared [1] and visible light [2]. Equally well developed are frequency selective surfaces [3–6], which are used as filters in radar systems, antenna technology [7], broadband communications, and terahertz technology [8, 9]. However, the range of optical effects observable in planar metamaterials and the variety of potential applications have only become clear since metamaterials research took off in 2000 [10]. Wave plate [11, 12] as well as polarization rotator and circular polarizer [13–15] functionalities have been demonstrated in metamaterials of essentially zero thickness. Traditionally, such components are large as they rely on integrating weak effects over thick functional materials. Polarization rotation has also been seen at planar chiral diffraction gratings [16, 17] and thin layered stereometamaterials [18, 19]. Electromagnetically induced transparency (EIT) [20–24] and high quality factor resonances [20] have been observed at planar structured interfaces. And finally, new fundamental electromagnetic effects leading to directionally asymmetric transmission of circularly [25–29] and linearly polarized waves have been discovered in planar metamaterials.
Planar metamaterials derive their properties from artificial structuring rather than atomic or molecular resonances, and therefore appropriately scaled versions of such structures will show similar properties for radio waves, microwaves, terahertz waves, and, to some extent, in the infrared and optical spectral regions where losses are becoming more important.
By
Peter B. Catrysse, Stanford University, Stanford, CA 94305, USA,
Hocheol Shin, Stanford University, Stanford, CA 94305, USA,
Shanhui Fan, Stanford University, Stanford, CA 94305, USA
All-angle negative refraction of electromagnetic waves [1, 2] has generated great interest because it provides the foundation for a wide range of new electromagnetic effects and applications, including subwavelength image formation [2] and a negative Doppler shift [1], as well as novel guiding, localization and nonlinear phenomena [3, 4]. There has been tremendous progress in achieving negative refraction in recent years using either dielectric photonic crystals [5–9] or metallic meta-materials [10–17]. For either approach, however, there is an underlying physical length scale that sets a fundamental limit [18]. Below such a length scale, the concept of an effective index no longer holds. For photonic crystals, it is the periodicity, which is smaller than but comparable to the operating wavelength of light [8]. For metallic meta-materials, it is the size of each individual resonant element. In the microwave wavelength range, constructing resonant elements that are far smaller than the operating wavelength is relatively straightforward. As one pushes towards shorter optical wavelengths, however, it becomes progressively more difficult to construct resonant elements at a deep subwavelength scale [15]. Moreover, in the optical wavelength range, the plasmonic effects of metals become prominent. The strong magnetic response of metallic structures, as observed in microwave and infrared wavelength ranges, may be fundamentally affected. It is therefore very desirable to accomplish all-angle negative refraction using structures that are flat at an atomic scale.
Negative refraction (NR) has been theoretically predicted [1, 2] and experimentally realized [3–7] in three types of materials. One is a material with a simultaneously negative permittivity and permeability [8–12], leading to a negative refractive index for the medium. The second consists of a photonic crystal (PhC) [13–21], which is a periodic arrangement of scatterers in which the group and phase velocities can be in different directions leading to NR. The third is the indefinite medium [22–28], whose permittivity and/or permeability tensor is an indefinite matrix. In all cases, the bulk properties of the medium, which is inherently inhomogeneous at a subwavelength scale, can be described as having an effective negative refractive index. The active research in these artificial materials has opened doors to a plethora of unusual electromagnetic properties and new applications such as a perfect lens [29], subwavelength imaging [30], cloaking [31], slow light, and optical data storage [32, 33], that cannot be obtained with naturally occurring materials. The holy grail of manufacturing these artificial photonic metamaterial structures is to manipulate light at the nanoscale level for optical information processing and high-resolution imaging.
In order to achieve NR, engineering the bulk electromagnetic properties is normally needed such that the group velocity and phase velocity be at an obtuse angle or even anti-parallel to each other. However, refraction is a surface phenomenon. A bulk-engineered material will have certain inherent surface properties. Negative refraction can be realized in positive index materials by special orientation or by engineering the interface properties.
By
A. I. Fernández-Domínguez, Universidad Autonoma de Madrid, E-28049 Madrid, Spain,
F. García-Vidal, Universidad Autonoma de Madrid, E-28049 Madrid, Spain,
L. Martín-Moreno, Universidad de Zaragoza, E-500009 Zaragoza, Spain
The ability to localize electromagnetic energy below the diffraction limit of classical optics featured by surface plasmon polaritons (SPPs) (electromagnetic surface waves sustained at the interface between a conductor and a dielectric) is currently being exploited in numerous studies ranging from photonics, optoelectronics, and materials science to biological imaging and biomedicine [1]. While the basic physics of SPPs has been described in a number of seminal papers spanning the twentieth century [2, 3], the more recent emergence of powerful nanofabrication and characterization tools has catalyzed a vast interest in their study and exploitation. The dedicated field of plasmonics [4] brings together researchers and technologists from a variety of disciplines, with the common aim to take advantage of the subwavelength light confinement associated with the excitation of SPPs.
Most interest is focused on the optical regime, where SPPs are strongly confined to the respective metal/dielectric interface, i.e. where subwavelength mode localization is achieved in the direction perpendicular to the interface. These strongly confined SPPs occur at frequencies which are still an appreciable fraction of the intrinsic plasma frequency of the metal in question. In this regime, the motion of the conduction electrons at the interface is dephased with respect to the driving electromagnetic fields, leading to a reduction in both phase and group velocities of the SPP, and, therefore, to strong localization. A considerable fraction of the SPP field energy resides inside the conductor.
Nanotechnology has seen enormous progress in recent years, and various techniques are now available for the realization of ordered periodic arrays of particles with nanoscale dimensions. Electron-beam [1] and interference lithography [2], polymer-based nanofabrication [3], and self-assembly techniques [4] indeed enable producing ordered one-dimensional (1-D), two-dimensional (2-D), and even three-dimensional (3-D) arrays of metallic or dielectric nanoparticles with sizes much smaller than the wavelength of operation. As is well established in the field of optical metamaterials, such arrays may interact with light in anomalous and exotic ways, provided that their unit cells are sufficiently close to the individual or collective resonance of these arrays.
The electromagnetic response of optical metamaterials and metasurfaces is very distinct from that of gratings and photonic crystals. In photonic crystals, for which lattice periods are comparable to the wavelength of operation, it is possible to tailor the optical interaction operating near the Bragg collective resonances and Wood's anomalies associated with their period, whereas in optical metamaterials and metasurfaces, we operate near the plasmonic resonances of the individual inclusions, leading to the advantage of a much broader response in terms of the angle of incidence, and the absence of grating lobes in the visible angular spectrum. On the other hand, unlike photonic crystals, optical metamaterials and metasurfaces require a much smaller scale for their unit cells. Moreover, plasmonic materials, required to support the required resonances at the nanoscale, are usually characterized by intrinsic non-negligible loss and absorption.