Gradient silver nanoparticle layers in absorbing coatings--experimental study

Metal island films show a characteristic absorption peak related to the surface plasmon resonance of free electrons. This kind of film can be used in absorbing coatings, together with dielectric layers. Such absorbing multilayer coatings, with and without the gradient of the silver mass thickness in metal island films throughout the coating, have been deposited by electron beam evaporation. It is shown experimentally that coatings with a gradient in the mass thickness of silver nanoparticles have higher absorption than equivalent nongradient coatings with the same total mass thickness of silver nanoparticles.     

Optical encoding by plasmon-based patterning: hard and inorganic materials become photosensitive

The photosensitivity of nanocomposite AlN films with embedded silver nanospheres is reported. It stems from localized surface plasmon resonances (LSPR) whose modulation is photoinduced by laser annealing that induces a combined effect of metallic nanoparticle enlargement and dielectric matrix recrystallization; the photoindunced changes of the refractive index of the matrix result in strong spectral shift of LSPR. We demonstrate the utilization of this process for spectrally selective optical encoding into hard, durable, and chemically inert films.     

Hochselektive Absorberschichten für thermische Sonnenkollektoren

High‐selective absorber coatings for solar thermal collectors Highly selective absorber coatings are necessary for the effective operation of state‐of‐the‐art solar thermal collectors. The thin film gradient optical coating with its spectrally selective characteristics achieves high solar absorptance combined with low thermal emittance. Such complex multi‐layer systems are produced in modular vacuum coating processes. Industrial air‐to‐air coating lines allow the continuous coating of metal bands in a pass‐through process and provide absorber coatings which meet highest demands for efficiency, durability and esthetics.     

Materials for solar-transmitting heat-reflecting coatings

A coating for solar energy applications which combines heat reflection with transparency to solar radiation may be of four different types: a metallic film which is sufficiently thin to be transparent; a metal-based multilayer coating; a wide band gap heavily doped semiconductor such as SnO₂ or In₂O₃; a conducting microgrid. We prepared such coatings on glass by evaporating thin films of silver, copper, gold, aluminium, cobalt, iron, chromium and nickel of various thicknesses and by spraying SnO₂ films. The spectral variations in the transmittance, and the front side and back side reflectances were measured in the wavelength range 0.4–15 μm. The properties of a three-layer coating of the dielectric/metal/dielectric type were calculated with a multilayer program using known bulk optical constants. The effect of these films when coated onto a domestic window was demonstrated with a heat transfer calculation using an equivalent thermal net. When a large transmittance over a broad range of the solar spectrum is required, gold is an equally good, or a slightly better, choice than silver as the metal in a three-layer coating. In general, an SnO₂ film exhibits a higher solar transmittance as well as a higher emittance than a coating containing metals. This implies that the oxide is to be preferred as a coating on a window when the maximum passive solar heating is sought. However, a metal-based coating could be better when a very low U_L value is the most important requirement.     

Optical properties of gold island films—a spectroscopic ellipsometry study

Metal island films of noble metals are obtained by deposition on glass substrates during the first stage of evaporation process when supported metal nanoparticles are formed. These films show unique optical properties, owing to the localized surface plasmon resonance of free electrons in metal nanoparticles. In the present work we study the optical properties of gold metal island films deposited on glass substrates with different mass thicknesses at different substrate temperatures. The optical characterization is performed by spectroscopic ellipsometry at different angles of incidence and transmittance measurements at normal incidence in the same point of the sample. Fitting of the ellipsometric data allows determining the effective optical constants and thickness of the island film. A multiple oscillator approach was used to successfully represent the dispersion of the effective optical constants of the films.     

Quasicrystal films: numerical optimization as a solar selective absorber

Selective absorbers for solar thermal energy applications have to show high solar absorptance _s and low thermal emittance ε_h. Stability against oxidation and diffusion is indispensable, especially at high absorber temperatures. The new class of quasicrystalline materials seems to have favourable properties regarding stability. With a genetic algorithm a thin film stack based on dielectric and quasicrystal films was optimized as a selective absorber. A sandwich system dielectric/quasicrystal/dielectric on copper has highly selective properties: _s = 0.86 and ε_h (400 °C) = 0.051. Even better results can be achieved, at least in theory, by the use of a cermet. The optical constants of cermets with the quasicrystalline material as the metal were calculated with the Bruggeman theory. A system of a cermet film and an additional antireflective coating on copper shows _s = 0.92 and ε_h (400 °C) = 0.048.     

Optical properties of silver sulphide thin films formed on evaporated Ag by a simple sulphurization method

Silver sulphide (Ag₂S) thin films were grown on the surface of silver films (Ag) deposited on glass substrate by using a simple chemical sulphurization method. According to X-ray diffraction analysis, the Ag₂S thin films display low intensity peaks at 34.48°, 36.56°, and 44.28°, corresponding to diffraction from (100), (112) and (103) planes of the acanthite phase (monoclinic). A model of the type Ag₂S/Ag/glass was deduced from spectroscopic ellipsometric measurements. Also, the optical constants (n, k) of the system were determined. Furthermore, the optical properties as solar selective absorber for collector applications were assessed. The optical reflectance of the Ag₂S/Ag thin film systems exhibits the expected behavior for an ideal selective absorber, showing a low reflectance in the wavelength range below 2 µm and a high reflectance for wavelengths higher than that value. An absorptance about 70% and an emittance about 3% or less were calculated for several samples.     

Radiation filters and emitters for the NIR based on periodically structured metal surfaces

Abstract

The spectrally selective optical properties of wavelength selective radiation emitters and filters based on periodically microstructured metal surfaces were investigated. Metal surfaces were structured by the use of a holographic mask and subsequent etching processes. Due to the microstructure, thermally excited surface plasmons couple to electromagnetic radiation. Therefore a structured tungsten surface can act as a selective radiation emitter. The calculation of the absorptance by a rigorous diffraction theory allows the prediction of the emissivity of such structures. The angle dependent emissivity of tungsten gratings with periods of 1.4 μm and 2.0 μm was measured. A peak emissivity of 70% at a wavelength of 1.6 μm was achieved. Band pass filters for the near infrared spectral range based on perforated metal films were investigated theoretically and experimentally. Filters with a grating period of 2.0 μm were produced. A peak transmittance of 80% at a wavelength 2.9 μm was achieved. The optical properties of the diffractive elements described partly show a strong angle dependence     

Tunable near-infrared epsilon-near-zero and plasmonic properties of Ag-ITO co-sputtered composite films

Series of co-sputtered silver-indium tin oxide (Ag-ITO) films are systematically fabricated. By tuning the atomic ratio of silver, composite films are manifested to have different microstructures with limited silver amount (<3 at.%). Two stages for film morphology changing are proposed to describe different status and growth mechanisms. The introduction of silver improves the preferred orientations of In₂O₃ component significantly. Remarkably, dielectric permittivity of Ag-ITO films is highly adjustable, allowing the cross-over wavelengths λ_c to be changed by more than 300 nm through rapid post-annealing, and thus resulting in tunable epsilon-near-zero and plasmonic properties in the near-infrared region. Lower imaginary permittivity compared with pure metal films, as well as larger tunability in λ_c than pure ITO films suggest the potentiality of Ag-ITO films as substituted near-infrared plasmonic materials. Extended Maxwell-Garnett model is applied for effective medium approximation and the red-shifting of epsilon-near-zero region with the increase of silver content is well-fitted. Angle-variable prism coupling is carried out to reveal the surface plasmon polariton features of our films at optical communication wavelength. Broad dips in reflectance curves around 52–56° correspond to the SPP in Ag-ITO films.     

Preparation of solar selective absorbing coatings by magnetron sputtering from a single stainless steel target

This paper presents a method to prepare solar selective absorbing coatings by radio frequency magnetron reactive sputtering using a single stainless steel target. Stainless steel/stainless steel nitride (SS/SS-N) ceramic-metal composite (cermet) thin films were produced under varied nitrogen gas flow ratios. The solar selective absorbing films have good solar absorptance of 0.91 and thermal emittance of 0.06 at 82 °C. The refractive index (n) and extinction coefficient (k) of the cermet composite layers prepared in nitrogen and argon atmospheres were determined by spectroscopic ellipsometry. The films were also analyzed by different oscillator models. The results showed a significant transformation from metal to cermet as the nitrogen gas flow ratio was increased to 10%. As the nitrogen gas flow ratio was increased to 17.5%, the film became a dielectric layer that could be used as an anti-reflection layer, suitable as the outermost layer of the solar selective absorbing coatings. A theoretical solar absorptance of 0.92 was achieved by selecting an appropriate combination of three solar absorbing layers. The experimental results agreed well with the theoretical calculations. This study proved the possibility of preparing solar selective absorbing coatings with high solar absorptance by using a single stainless steel target.     

Optical properties of Ag -TiO 2 nanocermet films prepared by cosputtering and multilayer deposition techniques

Ag -TiO2 nanocermet thin films, deposited for optical filtering applications by two sputtering techniques, codeposition and multilayer deposition, exhibit surface plasmon absorption in the spectral range 450 -500 nm. The cosputtering technique induces a columnar growth, whereas multilayer deposition produces a more-random distribution of silver inclusions. Both films have large, flat silver grains at the air -cermet interface. An optical double-heterogeneous layer model based on the experimental morphological parameters of the films accounts well for their experimental transmittance, notably for extra absorption near 700 nm, which is attributed to a surface plasmon in the flat silver grains of the surface.     

Optical Properties of Ag-TiO(2) Nanocermet Films Prepared by Cosputtering and Multilayer Deposition Techniques

Ag-TiO(2) nanocermet thin films, deposited for optical filtering applications by two sputtering techniques, codeposition and multilayer deposition, exhibit surface plasmon absorption in the spectral range 450-500 nm. The cosputtering technique induces a columnar growth, whereas multilayer deposition produces a more-random distribution of silver inclusions. Both films have large, flat silver grains at the air-cermet interface. An optical double-heterogeneous layer model based on the experimental morphological parameters of the films accounts well for their experimental transmittance, notably for extra absorption near 700 nm, which is attributed to a surface plasmon in the flat silver grains of the surface.     

Diffraction-based tracking of surface plasmon resonance enhanced transmission through a gold-coated grating

Surface plasmon resonance enhanced transmission through metal-coated nanostructures represents a highly sensitive yet simple method for quantitative measurement of surface processes and is particularly useful in the development of thin film and adsorption sensors. Diffraction-induced surface plasmon excitation can produce enhanced transmission at select regions of the visible spectrum, and wavelength shifts associated with these transmission peaks can be used to track adsorption processes and film formation. In this report, we describe a simple optical microscope-based method for monitoring the first-order diffracted peaks associated with enhanced transmission through a gold-coated diffraction grating. A Bertrand lens is used to focus the grating's diffraction image onto a CCD camera, and the spatial position of the diffracted peaks can be readily transformed into a spectral signature of the transmitted light without the use of a spectrometer. The surface plasmon peaks appear as a region of enhanced transmission when the sample is illuminated with p-polarized light, and the peak position reflects the local dielectric properties of the metal interface, including the presence of thin films. The ability to track the position of the plasmon peak and, thus, measure film thickness is demonstrated using the diffracted peaks for samples possessing thin films of silicon oxide. The experimental results are then compared with calculations of optical diffraction through a model, film-coated grating using the rigorously coupled wave analysis simulation method.     

Optical switch from silver nanocomposite thin films

Silver nanoparticles capped with sodium alginate were assembled into thin films by using the layer-by-layer dipping technique. Composite films were built by sequential dipping of a glass slide in either anionic alginate capped nanoparticles or cationic Poly(diallyldimethylammonium chloride) (PDADMAC). The growth of the film was characterized using UV-Vis spectroscopy by monitoring the increase in absorbance at 420 nm which correspond to the silver nanoparticles plasmon band. The final films formed onto glass slides displayed and interesting color shift upon exposure to water or to a less polar solvent such as ethanol. In this research, changes in spectral absorbance of the nanoparticles film were monitored as a function of ethanol content (0, 20, 40, 60, 80 and 100%) in water. The color shift from yellow to red color was explained by the changes in the dielectric constant of the silver nanoparticles surrounding medium which induce a shift in their plasmon band absorbance. These composite thin films displayed fast color change and could therefore be used in sensing application as well as for optical switches.     

Structure-Related Optical Characteristics of Thin Metallic Films in the Visible and Ultraviolet

Surface irregularities and crystalline order strongly influence both the scattered light and absorption of metallic films. These effects extend through all spectral regions but are particularly important in the visible and ultraviolet. Scattered light arises from several scattering mechanisms. Macroscopic irregularities such as dust, scratches and particulates are typically much less important than are microirregularities only a few tens of angstroms in height but covering the entire surface. For metals such as silver and aluminum, which have plasma edges in the ultraviolet, the excitation of surface plasmons resulting from these microirregularities causes additional incoherently reemitted or “scattered” light. Surface plasmon excitation also causes increased absorption in some wavelength regions. These effects are enhanced by dielectric overcoating layers, which both increase the absorption and scattering and shift the wavelength at which the peak occurs. Surface plasmon excitation is particularly important in the ultraviolet region, where the dielectric overcoating applied to prevent formation of an oxide film on aluminized mirrors, for example, can significantly change the mirror reflectance. Plasmon excitation is made possible by a momentum conserving process associated with material inhomogeneities and hence can presumably be caused by crystalline disorder in the metal surface as well as surface irregularities. If the disorder is present on a sufficiently fine scale, it also affects the band structure of the metal and hence its optical absorption. Examples of the effect of film structure on the optical properties of evaporated and sputtered metal films will be given.     

Reflection and Absorption Techniques for Optical Characterization of Chemically Assembled Nanomaterials

This review discusses recent developments in the areas of fabrication, certain types of optical characterization, and applications of a selected class of chemically assembled nanomaterials, namely i) gold and silver nanoparticles deposited onto optically transparent glass substrates; ii) thiol‐functionalized self‐assembled monolayers (SAMs); iii) chemically stabilized gold and silver nanoparticles (monolayer protected clusters, MPCs); and iv) MPCs linked to metallic substrates and adsorbates. Six linear optical techniques for the characterization of these materials are discussed: transmission localized surface plasmon resonance spectroscopy, T‐LSPR; propagating surface plasmon resonance spectroscopy, P‐SPR; polarization‐selective Fourier transform infrared reflection absorption spectroscopy, PS‐FTIRRAS; polarization‐modulation Fourier transform infrared reflection absorption spectroscopy, PM‐FTIRRAS; surface‐enhanced infrared reflection absorption spectroscopy, SEIRRAS; and infrared ellipsometry. The review focuses particularly on providing a unified treatment of these six optical techniques by using a relatively simple stratified multilayer model.     

Alte Faustregeln für das Design optischer Schichtsysteme

Old rules useful to the designer of optical coatings Optical coatings are usually composed of multilayer film structures which are used to obtain a desired transmittance, reflectance and absorptance from a surface. The spectral characteristic may be due to the intrinsic property of the material (e.g. metal reflectors) or due to interference effects arising from the multilayer stack. The following is a set of guidelines (“old rules”) useful to the designer of optical systems of which coated surfaces are an integral part.     

Dielectric and optical properties of CaCu3Ti4O12 thin films containing Ag nanoparticles

Simple sol-gel techniques are used to prepare thin films of a high dielectric constant perovskite CaCu₃Ti₄O₁₂, containing different amounts of metallic silver nanoparticles. The formations of the silver nanoparticles are verified by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and optical absorption studies. The dielectric properties are found to be significantly affected by the presence of the silver nanoparticles. A maximum in the dielectric constant is observed at an intermediate metal particle concentration. This is explained in terms of the polarization at the particle-dielectric interface and the internal barrier layer capacitor effect. The optical absorption spectrum is compared with Mie theory in electrodynamics for the optical absorption of small particles to extract the particle size of the silver particle. Non-uniform distributions of Ag particles through the thickness of the thin films are reported.     

A broadband analysis of the optical properties of silver nanoparticle films by in situ real time spectroscopic ellipsometry

A broadband analysis of the optical properties of silver nanoparticle films over the range from 0.75 to 6.5 eV was performed by applying in situ real-time spectroscopic ellipsometry (RTSE) during the nucleation, coalescence, and bulk thin film growth regimes. The dielectric functions of the particulate films were found to depend strongly on the particle size and film thickness from the nucleation regime throughout coalescence. These dependences were analyzed by separately characterizing the three types of transitions evident in the dielectric function: intraband, particle plasmon polariton, and interband. Throughout the film growth regimes, the thickness evolution of the amplitude, energy, and broadening parameter for each type of transition is discussed in view of the structural characteristics of the films, as corroborated ex situ by atomic force microscopy for films deposited over different time durations.     

Magnetron Sputtering Deposition of Ag/TiO2 Nanocomposite Thin Films for Repeatable and Multicolor Photochromic Applications on Flexible Substrates

It is reported on a reactive magnetron sputtering‐based deposition method to synthesize, at room temperature, photochromic nanocomposite thin films consisting of Ag nanoparticles sandwiched between nanoporous TiO₂ layers. The fabrication process is compatible with large‐scale production and functional flexible substrates. It is shown that when TiO₂ is deposited in the metallic mode, the formation of Ag metal nanoparticles induces localized surface plasmon resonances in the visible range and therefore the as‐deposited samples are colored. In contrast, when TiO₂ is deposited in the compound mode, the trilayer samples are colorless because silver oxidizes during TiO₂ deposition. It is demonstrated that the colorless samples can be colored under ultraviolet (UV) laser exposure at 244 nm due to the reduction of oxidized silver and the formation of metallic Ag nanoparticles. Moreover, irradiation at 647 nm wavelength of colored samples (as‐prepared or after UV exposure) gives rise to changes in the particle morphology that strongly modifies the film absorbance and results in a color transition from blue to orange. The choice of the irradiation wavelength allows controlling the color saturation of the sample up to the complete discoloration by using a visible laser at 488 nm. All these photochromic mechanisms are repeatable during cyclic processes.