Noble Metal Thin Films Research Articles

Study the Optical Properties of Noble Metal (Au, Ag, and Cu) Thin Film Biosensors Based on Surface Plasmon Resonance Performance by a Simulation Program

In this work, we studied the effect noble metal thicknesses, namely gold (Au), silver (Ag), and copper (Cu) on the surface plasmon resonance (SPR) characteristics for sensitive optical sensor and biosensor applications. SPR spectra for Au, Ag and Cu were widely studied in the Fresnel equation to calculate the total reflection, the wavelength ([Formula: see text] range from 500 nm to 700 nm with the angle of incidence ([Formula: see text] ranging from 0∘ to 90∘ and thickness of the film ([Formula: see text] reaching from 30 nm to 70 nm. Analysis simulation (in MATLAB) has been made for SPR of three metals placed on the N_LASF9 glass prism and the sensing medium is the air. The properties of the angle of resonance [Formula: see text] have been calculated from plotted reflectance via incident angle [Formula: see text]. The results give efficient detection in a change of reflection ([Formula: see text] and full half width maximum FWHM. The minimum reflection was obtained (0.003 a.u.) at wavelength 700 nm and thickness [Formula: see text]= 50 nm for gold Au at [Formula: see text] = 0.0. The best FWHM was recorded at the wavelength (500 nm) at thickness (70 nm) for silver at [Formula: see text] = 0.0, which was equal (0.1 nm).

Combining physical vapor deposition structuration with dealloying for the creation of a highly efficient SERS platform.

Nanostructured noble metal thin films are highly studied for their interesting plasmonic properties. The latter can be effectively used for the detection of small and highly diluted molecules by the surface-enhanced Raman scattering (SERS) effect. Regardless of impressive detection limits achieved, synthesis complexity and the high cost of gold restrict its use in devices. Here, we report on a novel two-step approach that combines the deposition of a silver-aluminum thin film with dealloying to design and fabricate efficient SERS platforms. The magnetron sputtering technique was used for the deposition of the alloy thin film to be dealloyed. After dealloying, the resulting silver nanoporous structures revealed two degrees of porosity: macroporosity, associated to the initial alloy morphology, and nanoporosity, related to the dealloying step. The resulting nanoporous columnar structure was finely optimized by tuning deposition (i.e., the alloy chemical composition) and dealloying (i.e., dealloying media) parameters to reach the best SERS properties. These are reported for samples dealloyed in HCl and with 30 atom % of silver at the initial state with a detection limit down to 10-10 mol·L-1 for a solution of rhodamine B.

Nanoscale ITO Films for Plasmon Resonance-Based Optical Sensors

The developing field of plasmonics has led to the possibility of creating a new type of high-speed, highly sensitive optical sensors for the analysis of chemical and biological media. The functional conducting layers of surface plasmon resonance (SPR) optical sensors are almost always nanoscale thin films of noble metals. To enhance the plasmon resonance, nanostructured films of transparent conductive oxides are introduced into the optical sensors. However, such modified optical sensors operate in the infrared region of the spectrum. In this work, we demonstrate that the use of indium tin oxide (ITO) films with a high concentration of charge carriers makes it possible to shift the surface plasmon resonance into the visible radiation region. The work presents the results of the development of magnetron deposition technology for ITO thin films, with optimal parameters for optical sensors based on surface plasmon resonance operating in the visible range of the spectrum. Their optical and electrical characteristics are investigated. Excitation of the surface and volume plasmon resonance at the dielectric-ITO film interface, using the Kretschman configuration, is studied. It is shown that SPR is excited in the investigated ITO films with a concentration of free charge carriers of the order of 1021–1022 cm−3, when irradiated with a beam of light with TM polarization in the wavelength range of 350–950 nm. At the same time, the addition of various analytes to the surface of an ITO film changes the excitation wavelength of the SPR.

Implementation of Ag/ SiO2 nanofilms for metamaterial engineering

Low dimensions of the nanostructured thin films are essential in applications of miniaturized optical systems. Noble metal thin films of different thicknesses (4–10 nm) were obtained by radio frequency magnetron sputtering (rfMS) with controlled morphology. They exhibit optical behavior useful to metamaterial structures with possible applications in space industry. Optimized deposition conditions led to thin films with a good surface morphology, consisting of nanoparticles with dimensions between 6 nm and 11 nm and a surface roughness between 0.7 nm and 1.5 nm, determined by atomic force microscopy measurements. The thickness of thin films was predefined and monitored in situ with a quartz balance, and the deposition rate was 1.6 Å/s – 1.7 Å/s. High-resolution scanning electron microscopy was used to analyze the surface topography of the samples, showing that Ag thin films are uniform and continuous. The analyzed general XPS scans, as well as, high resolution spectra showed the presence of Ag 3d3 and Ag3d5 in the silver nanostructures. XRD diffractograms indicated the Ag thin films are crystalline. It is also highlighted that increasing the thickness of Ag thin films improves the crystallinity of the corresponding thin film. The morphology changes are manifested in the displacement of the diffraction peak and in values of the grain size between 5.1 nm and 6.7 nm, respectively. The obtained Ag thin films have an adequate morphology and metamaterial-like properties.

High‐Capacitance Nanoporous Noble Metal Thin Films via Reduction of Sputtered Metal Oxides

AbstractIncreasing the electrochemical surface area of noble metal electrodes is vital for many applications, including catalysis and bioelectronics. Herein, a method is presented for obtaining porous noble metal thin films via reactive magnetron sputtering of noble metal oxides, MOx, followed by their reduction using chemical reducers or electrochemical current. Variation of reduction conditions yields a range of different electrochemical and morphological properties. This method for obtaining porous noble metals is rapid, facile, and compatible with microfabrication processes. The resulting metallic films are porous and have competitively high capacitance and low impedance.

Noble Metal Thin Film Thickness Optimization for Sharp Surface Plasmon Resonance Reflectance Curve

The production of a high-sensitivity surface Plasmon resonance (SPR) sensor depends on a few main factors, such as metal thin film types and thicknesses, light coupling techniques and acceptable EM wave polarization modes. This work is carried out to investigate the impact on the SPR characteristics of noble metal thicknesses, namely gold and silver, for optical sensor applications. To excite surface Plasmon polaritons (SPP), a Kretschmann prism coupling was used. The thicknesses of noble metal thin films were varied between t=30nm and 60nm. The characteristics of SPR peaks such as Q-factor and FWHM were studied in SPR signal analyses. In comparison with silver, Q-factor results showed an outstanding optical property of gold at t= 40 nm due to its high Q-factor values, which confirms its ability to produce excellent SPP quantities. In conclusion, gold noble metal at t= 40nm is capable of producing optimum SPR. In the development of the highly sensitive SPR sensor, this excellent criterion put gold as a spectacular candidate for optical sensor applications.

Gas Sensors Based on Localized Surface Plasmon Resonances: Synthesis of Oxide Films with Embedded Metal Nanoparticles, Theory and Simulation, and Sensitivity Enhancement Strategies

This work presents a comprehensive review on gas sensors based on localized surface plasmon resonance (LSPR) phenomenon, including the theory of LSPR, the synthesis of nanoparticle-embedded oxide thin films, and strategies to enhance the sensitivity of these optical sensors, supported by simulations of the electromagnetic properties. The LSPR phenomenon is known to be responsible for the unique colour effects observed in the ancient Roman Lycurgus Cup and at the windows of the medieval cathedrals. In both cases, the optical effects result from the interaction of the visible light (scattering and absorption) with the conduction band electrons of noble metal nanoparticles (gold, silver, and gold–silver alloys). These nanoparticles are dispersed in a dielectric matrix with a relatively high refractive index in order to push the resonance to the visible spectral range. At the same time, they have to be located at the surface to make LSPR sensitive to changes in the local dielectric environment, the property that is very attractive for sensing applications. Hence, an overview of gas sensors is presented, including electronic-nose systems, followed by a description of the surface plasmons that arise in noble metal thin films and nanoparticles. Afterwards, metal oxides are explored as robust and sensitive materials to host nanoparticles, followed by preparation methods of nanocomposite plasmonic thin films with sustainable techniques. Finally, several optical properties simulation methods are described, and the optical LSPR sensitivity of gold nanoparticles with different shapes, sensing volumes, and surroundings is calculated using the discrete dipole approximation method.

New features in the surface plasmon induced photon drag effect in noble metal thin films

We study light–matter interactions leading to the generation of photon drag voltage under surface plasmon resonance conditions in noble metal thin films and observe important effects, which provide opportunity for condensed matter theorists to critically evaluate theoretical models. The drag voltage originates from a force that arises because of the transfer of momentum from incident light to electrons. This transfer of photon momentum leads to an electric current, which in turn results in the generation of drag voltage. The effect is particularly enhanced under surface plasmon resonance conditions and thereby reinforces the interaction between light and collective oscillations of the surface charges. We observe relatively high voltages with a nonlinear dependence on laser intensity. In disagreement with previous results, we do not observe a reversal in the sign of the voltage when the direction of the incident laser momentum is reversed. Qualitative analyses of the data show that the hydrodynamic model of laser-induced drag voltage does not work: the hydrodynamic model predicts voltages that are nine orders of magnitude lower than our measurements. However, there is reasonable consistency between the results of the measurements and numerical simulations.

Strong Coupling, Hyperbolic Metamaterials and Optical Tamm States in Layered Dielectric-Plasmonic Media

Thin films of noble metals with thickness smaller than the wavelength of light constitute one of the most investigated structures in plasmonics. The fact that surface plasmon modes can be excited in these films by different ways and the simplicity of fabrication offer ideal conditions for applications in nanophotonics. The generation of optical modes in coupled Fabry-Pérot planar cavities and their migration to hyperbolic metamaterials is investigated. Coupled Fabry-Pérot cavities behave as simple coupled resonators. When the intra-cavity media have different refractive indices in two or more coupled cavities resonance anti-crossings arise. The application of this kind of strong coupling in sensing is foreseen. Beyond the cavity modes excited by propagating waves, also long range plasmonic guided modes can be excited using emitters or evanescent waves. A periodic structure made by multiple plasmonic films and dielectrica supports bulk plasmons, of large propagation constant and increasing field amplitude. The optical response of these structures approaches that of the hyperbolic metamaterial predicted by the effective medium theory. Light can propagate with full transmission in a structure made of a photonic crystal based on quarter wavelength layers and a second photonic crystal with an overlapping forbidden band, but presenting a non-trivial topological phase achieved by band inversion. This is due to excitation of optical Tamm states at the boundary between both crystals. The extension to multiple optical Tamm states using dielectric and plasmonic materials and the symmetries of the edge states is investigated.

Three-step deposition process for improved nucleation of noble metal thin films

A three-step atomic layer deposition process tested with ruthenium could hold the key to creating continuous and smooth noble metal thin films.

Controlling Electrical Conduction through Noble Metal Thin Films by Surface Plasmon Resonance

We have conducted in situ measurements of the surface plasmons and electrical resistivity of noble metal thin films. We present results for the electrical resistivity of these materials as functions of the angle of incidence for p-polarized light of wavelength λ = 632 nm in the Kretschmann configuration optical system. We observe a significantly lower resistivity (higher conductivity) under resonance conditions for the surface plasmon polaritons. The resistivity data are supported by COMSOL simulations of the evanescent fields associated with the surface plasmons. We discuss the resistivity data in terms of the theoretical models, which suggest that the electrical conductivity of the transition metals is sensitive to Umklapp electron-electron scattering and attractive interactions between free electrons because of the screening of the d-band electrons by the s-band electrons.

Design of Transparent Conducting Plasmonic Metasurfaces and Theory of Impedance-Matched Metastructures

We propose and numerically demonstrate a low-loss deep-subwavelength plasmonic metasurface that exhibits strong optical transmission at near-infrared wavelengths and concomitantly high electrical conductivity. The efficient realization of these two contrasting functionalities without a severe trade-off establishes the proposed metasurface as a potential alternative for conventional transparent electrodes. In contrast to conventional strategies of focusing on free carrier concentration management, the present design decouples the optical and electrical functionalities to a large extent. While the requirements of low electrical contact resistance are facilitated by the presence of an unstructured noble metal thin film, the optical requirements are fulfilled by achieving a transmission resonance through judicious structural and dispersion engineering. The genesis of transmission resonance in our impedance-matched metastructure lies in the excitation of structure derived magnetic plasmon resonance and its coupling to the radiative mode of the underlying planar plasmonic multilayer system. Furthermore, we develop a generalized theoretical framework where we analytically derive the modal dispersion for the plasmonic structure and investigate for the existence of the aforementioned radiative modes. The analysis establishes the fact that for asymmetric multilayer plasmonic systems, the evanescent plasmonic mode can exhibit a mode cut-off and becomes a propagating mode in the high refractive index medium, thereby materializing the possibility of resonant transmission. This theoretical model will be instrumental in gaining crucial physical insights into the operation of plasmonic devices and help in identifying their domain of operation.

Scalable, Green Fabrication of Single-Crystal Noble Metal Films and Nanostructures for Low-Loss Nanotechnology Applications.

The confinement of spatially extended electromagnetic waves to nanometer-scale metal structures can be harnessed for application in information processing, energy harvesting, sensing, and catalysis. Metal nanostructures enable negative refractive index, subwavelength resolution imaging, and patterning through engineered metamaterials and promise technologies that will operate in the quantum plasmonics regime. However, the controlled fabrication of high-definition single-crystal subwavelength metal nanostructures has remained a significant hurdle due to the tendency for polycrystalline metal growth using conventional physical vapor deposition methods and the challenges associated with placing solution-grown nanocrystals in desired orientations and locations on a surface to manufacture functional devices. Here, we introduce a scalable and green wet chemical approach to monocrystalline noble metal thin films and nanostructures. The method enables the fabrication of ultrasmooth, epitaxial, single-crystal films of controllable thickness that are ideal for the subtractive manufacture of nanostructures through ion beam milling and additive crystalline nanostructure via lithographic patterning for large-area, single-crystal metasurfaces and high aspect ratio nanowires. Our single-crystal nanostructures demonstrate improved feature quality, pattern transfer yield, reduced optical and resistive losses, and tailored local fields to yield greater optical response and improved stability compared to those of polycrystalline structures-supporting greater local field enhancements and enabling practical advances at the nanoscale.

Towards maximized utilization of iridium for the acidic oxygen evolution reaction

The reduction in noble metal content for efficient oxygen evolution catalysis is a crucial aspect towards the large scale commercialisation of polymer electrolyte membrane electrolyzers. Since catalytic stability and activity are inversely related, long service lifetime still demands large amounts of low-abundant and expensive iridium. In this manuscript we elaborate on the concept of maximizing the utilisation of iridium for the oxygen evolution reaction. By combining different tin oxide based support materials with liquid atomic layer deposition of iridium oxide, new possibilities are opened up to grow thin layers of iridium oxide with tuneable noble metal amounts. In-situ, time- and potential-resolved dissolution experiments reveal how the stability of the substrate and the catalyst layer thickness directly affect the activity and stability of deposited iridium oxide. Based on our results, we elaborate on strategies how to obtain stable and active catalysts with maximized iridium utilisation for the oxygen evolution reaction and demonstrate how the activity and durability can be tailored correspondingly. Our results highlight the potential of utilizing thin noble metal films with earth abundant support materials for future catalytic applications in the energy sector.

Enhancement of plasmonic transmittance of porous gold thin films via gold/metal oxide bi-layers for solar energy-saving applications

Thin films of noble metals, such as gold, have high visible transparency and infrared reflectance. The former is due to the presence of surface plasmons, and the latter is due to the large density of free electrons. Gold thin films have a transmittance peak at 520 nm, which is closely matched to the maximum emission of solar radiation. These properties have been utilized in several applications, including energy-saving transparent heat mirrors that consist of a bi-layer of a thin gold film over-coated with a dielectric layer. These coatings transmit light and reflect heat. For such an application, the transmittance of the thin gold film needs to be enhanced; this is achieved by the dielectric layer that functions as an antireflective coating. In this work, the dielectrics were metal oxides that are transparent in the visible range. The selection criteria based on the band gap, and refractive index were first imposed to identify potential metal oxides. This resulted in the choice of ten metal oxides (CeO2, HfO2, MoO3, Nb2O5, NiO, SnO2, Ta2O5, TiO2, WO3, and ZrO2). The bi-layer performance was then optimized theoretically. The gold-metal oxide layers were subsequently fabricated, and their optical spectra were measured over the ultraviolet–visible-near infrared ranges. The performance of the heat mirrors was assessed in terms of their visible and solar transmittance and reflectance. A figure of merit was defined to evaluate the suitability of the oxides. The optical properties suggest that tungsten oxide (WO3) is the best oxide; however, hafnium oxide (HfO2) has the best performance for solar energy applications.

Splitting of Shockley surface states in thin films of noble metals

The splitting of the surface bands of Cu(1 1 1), Ag(1 1 1), and Au(1 1 1) films is studied by means of relativistic density-functional theory (DFT) calculations. It is found that the splitting of the bands of clean films obtained in semirelativistic approximation, in agreement with previous studies, stems from the interaction between the surfaces and hence depends on the thickness of the slabs. Since the Kramers’ degeneracy is not broken by the presence of the surface, the spin-orbit coupling does not lead to the spin-splitting of the bands. An H monolayer, deposited on one face of the film, breaks the inversion symmetry and results in the appearance of the Rashba-type splitting of the bands.

Electroless Deposition of Pb Monolayer: A New Process and Application to Surface Selective Atomic Layer Deposition.

The present work demonstrates an electroless (e-less) deposition of Pb monolayer on Au and Cu surface whose morphology and properties resemble its underpotentially deposited counterpart. Our results and analysis show that the e-less Pb monolayer deposition is a surface selective, surface controlled, self-terminating process. Results also show that the electroless Pb monolayer deposition is enabling a phenomenon for new deposition method called "electroless atomic layer deposition" (e-less ALD). Here, the e-less Pb monolayer serves as reducing agent and sacrificial material in surface limited redox replacement reaction with noble metal ions such as Pt n+, i.e., Pt deposition. The e-less ALD is highly selective to the metal substrates at which Pb forms the e-less monolayer. The full e-less ALD cycle leads to an overall deposition of a controlled amount of the noble metal. Repetition of the two-step e-less ALD cycle an arbitrary number of times leads to formation of a highly compact, smooth, and conformal noble metal thin film with applications spanning from catalyst synthesis to semiconductor technology. The process is designed for (but not limited to) aqueous solutions that can be easily scaled up to any size and shape of the substrate, deeming its wide applications.

Highly Reflective Mirror Based on Noble Metal 2D Babinet Metasurface

We study optical properties of plasmonic 2D nanostructures (metasurfaces) constructed by analogy with Babinet’s principle – combinations of a perforated noble metal thin film and a complementary array of nanodiscs. Despite of large absorption in either the perforated films or the arrays of nanodiscs, the considered metasurfaces were highly reflective. The effect of increased reflectance is attributed to mutual cancellation of electric and ‘magnetic’ dipoles induced in antiphase, thus suppressing absorption; and a spacer in between the dipoles influences the spectral and incidence angle ranges for the effect observation. We show that a chosen metasurface can have an angle- and polarization-independent response in a wide spectral range.

Transparent and conductive electrodes by large-scale nano-structuring of noble metal thin-films

The widespread use of transparent conductive films in modern display and solar technologies calls for engineering solutions with tunable light transmission and electrical characteristics. Currently, considerable effort is put into the optimization of indium tin oxide, carbon nanotube-based, metal grid, and nano-wire thin-films. The indium and carbon films do not match the chemical stability nor the electrical performance of the noble metals, and many metal films are not uniform in material distribution leading to significant surface roughness and randomized transmission haze. We demonstrate solution-processed masks for physical vapor-deposited metal electrodes consisting of hexagonally ordered aperture arrays with scalable aperture-size and spacing in an otherwise homogeneous noble metal thin-film that may exhibit better electrical performance than carbon nanotube-based thin-films for equivalent optical transparency. The fabricated electrodes are characterized optically and electrically by measuring transmittance and sheet resistance. The presented methods yield large-scale reproducible results. Experimentally realized thin-films with very low sheet resistance, Rsh = 2.01 ± 0.14 Ω/sq, and transmittance, T = 25.7 ± 0.08 %, show good agreement with finite-element method simulations and an analytical model of sheet resistance in thin-films with ordered apertures support the experimental results and also serve to aid the design of highly transparent conductive films. A maximum Haacke number for these 33 nm thin-films, ϕH = 10.7 × 10−3Ω−1 corresponding to T ≃ 80 % and Rsh ≃ 10 Ω/sq, is extrapolated from the theoretical results. Increased transparency may be realizable using thinner metal films trading off conductivity. Nevertheless, the findings of this article indicate that colloidal lithographic patterned transparent conductive films can serve as vital components in technologies with a demand for transparent electrodes with low sheet resistance.

Electroless UPD Monolayer Deposition - a Prelude to Highly Selective Electroless Atomic Layer Deposition Process

The improved understanding of nucleation kinetics has led to various discoveries in which the thin film growth was manipulated to enhance the evolution of atomically flat epitaxial overlayers. Exploiting some of these results has led to invention of several new methods and protocols for electrodeposition where underpotentially deposited (UPD) monolayer is used as a mediator, surfactant or sacrificial template. The one successful example is so called “deposition via surface limited redox replacement (SLRR) of UPD monolayer,” which gained a lot of applications for synthesis of noble metal thin films with different functionalities. This protocol/method represents the combination of the potential controlled step (formation of UPD monolayer) and the electroless step (SLRR of UPD monolayer by more noble metal ions, i.e., galvanic displacement). However, our studies show that there is still a lot of room left for improvements and further simplifications. These should expand application of this deposition protocol in many areas where traditional atomic layer deposition (ALD) process has been used. In this talk we present results demonstrating an electroless ALD process in which a Pb UPD monolayer is used as a reducing agent and sacrificial material in SLRR reaction with noble metal ions such as Pt, Pd, and Ru and Cu. The full deposition cycle involves sequential exposure of the substrate such as Cu and Ru to the solution for electroless Pb UPD monolayer deposition and then to the solution for SLRR reaction and noble metal deposition. This results in an overall deposition of controlled amount of noble metal which is the function of the areal density of deposited Pb monolayer and stoichiometry of the SLRR reaction. Therefore, the process mimics, to a great extent, the standard ALD cycle where adsorption of the metal precursors and surface catalyzed reaction are replaced by electroless Pb UPD monolayer deposition and SLRR reaction. If the two-step SLRR cycle is repeated an arbitrary number of times, a highly compact, smooth, and conformal noble metal thin film can be grown. The deposition process is highly selective to the metal substrates at which Pb forms an UPD monolayer providing an advantage when certain integration requirements are considered. The process is designed for (but not limited to) aqueous solutions with fairly simple and stable chemistry that can be easily scaled up to any size and shape of the substrate surface. Results demonstrating details and underlying phenomena controlling this process will be discussed. In addition, an example of a high quality of Pt, Pd, Cu and Ru films grown on Cu and Ru substrate will be shown, as well as the applications of this process for metallization of structures relevant to semiconductor device fabrication.