Film-metal interface

Let us imagine a piece of silver with an AgCl film to be immersed in a Cl solution. Two phase boundaries will form, one between the metal and the film and the other between the film and the solution. The interface metal/film is permeable for Ag but not for CP ions or electrons. It is impermeable to CP ions because they cannot be inserted into the metal lattice and electrons cannot pass through because silver chloride does not conduct electrons. Therefore, a Galvani potential difference will form there that is determined only by the chemical potentials of the Ag" ions in both phases. These are fixed values, so the Galvani potential difference will also have a fixed value. The interface film/solution is permeable to both CP and Ag" so that Ag and CP ions compete to set the Galvani potential difference. However, free Ag ions in a CP solution can only be present in extremely low concentrations, so they are hopelessly outnumbered by the CP ions. This is why only the CP ions determine the potential difference at this interface. 

Figure 4.29. Sample assembly for optical shock temperature measurements. The sample consists of a metal film deposited on a transparent substrate which serves as both an anvil and a transparent window through which thermal radiation is emitted. Rapid compression of gases and surface irregularities at the interface between the sample film and the driver produce very high temperatures in this region. The bottom portion of the figure illustrates the thermal distribution across through the assembly. (After Bass et al. (1987).)...

Figure 8 Quantitaftive high depth resolution profile of O and N in a Ti metal film on Si, using electron-gas SNMS in the direct bombardment mode. Both O and N are measured with reasonably good sensitivity and with good accuracy both at the heavily oxidized surface and at the Ti/Si interface.

The nature of the interface formed between very thin metallic films and substrates of various types has been studied extensively by AES, just as it has by XPS... 

Friedrich et al. also used XPS to investigate the mechanisms responsible for adhesion between evaporated metal films and polymer substrates [28]. They suggested that the products formed at the metal/polymer interface were determined by redox reactions occurring between the metal and polymer. In particular, it was shown that carbonyl groups in polymers could react with chromium. Thus, a layer of chromium that was 0.4 nm in thickness decreased the carbonyl content on the surface of polyethylene terephthalate (PET) or polymethylmethacrylate (PMMA) by about 8% but decreased the carbonyl content on the surface of polycarbonate (PC) by 77%. The C(ls) and 0(ls) spectra of PC before and after evaporation of chromium onto the surface are shown in Fig. 22. Before evaporation of chromium, the C(ls) spectra consisted of two components near 284.6 eV that were assigned to carbon atoms in the benzene rings and in the methyl groups. Two additional... 

When a solid electrolyte component is interfaced with two electronically conducting (e.g. metal) films (electrodes) a solid electrolyte galvanic cell is formed (Fig. 3.3). Cells of this type with YSZ solid electrolyte are used as oxygen sensors.8 The potential difference U R that develops spontaneously between the two electrodes (W and R designate working and reference electrode, respectively) is given by ... 

We start by considering a schematic representation of a porous metal film deposited on a solid electrolyte, e.g., on Y203-stabilized-Zr02 (Fig. 5.17). The catalyst surface is divided in two distinct parts One part, with a surface area AE is in contact with the electrolyte. The other with a surface area Aq is not in contact with the electrolyte. It constitutes the gas-exposed, i.e., catalytically active film surface area. Catalytic reactions take place on this surface only. In the subsequent discussion we will use the subscripts E (for electrolyte) and G (for gas), respectively, to denote these two distinct parts of the catalyst film surface. Regions E and G are separated by the three-phase-boundaries (tpb) where electrocatalytic reactions take place. Since, as previously discussed, electrocatalytic reactions can also take place to, usually,a minor extent on region E, one may consider the tpb to be part of region E as well. It will become apparent below that the essence of NEMCA is the following One uses electrochemistry (i.e. a slow electrocatalytic reaction) to alter the electronic properties of the metal-solid electrolyte interface E. 

This perturbation is then propagated via the spatial constancy of the Fermi level Ef throughout the metal film to the metal-gas interface G, altering its electronic properties thus causing ion migration and thus influencing catalysis, i.e. catalytic reactions taking place on the metal-gas interface G. 

We consider the adsorption of a single molecule, j, on a metal film M. The film is deposited on a solid electrolyte, e.g. YSZ, or is partly covered by a promoter, or simply has a significant coverage of adsorbed reactants and products on its surface, so that we may consider (Chapter 5) that an effective double layer is present at the the metal-gas interface (Fig. 6.15). 

Johans et al. derived a model for diffusion-controlled electrodeposition at liquid-liquid interface taking into account the development of diffusion fields in both phases [91]. The current transients exhibited rising portions followed by planar diffusion-controlled decay. These features are very similar to those commonly observed in three-dimensional nucleation of metals onto solid electrodes [173-175]. The authors reduced aqueous ammonium tetrachloropalladate by butylferrocene in DCE. The experimental transients were in good agreement with the theoretical ones. The nucleation rate was considered to depend exponentially on the applied potential and a one-electron step was found to be rate determining. The results were taken to confirm the absence of preferential nucleation sites at the liquid-liquid interface. Other nucleation work at the liquid-liquid interface has described the formation of two-dimensional metallic films with rather interesting fractal shapes [176]. 

Continuous (barrier, passivation) films have a high resistivity (106Q cm or more), with a maximum thickness of 10 4cm. During their formation, the metal cation does not enter the solution, but rather oxidation occurs at the metal-film interface. Oxide films at tantalum, zirconium, aluminium and niobium are examples of these films. 

Recently a novel experimental approach using Schottky diodes with ultra-thin metal films (see Fig. 11) makes direct measurement of reaction-induced hot electrons and holes possible. See for example Refs. 64 and 65. The chemical reaction creates hot charge carriers which travel ballistically from the metal film towards the Schottky interface and are detected as a chemicurrent in the diode. By now, such currents have been observed during adsorption of atomic hydrogen and deuterium on Ag, Cu and Fe surfaces as well as chemisorption of atomic and molecular oxygen, of NO and N02 molecules and of certain hydrocarbons on Ag. Similar results have been found with metal-insulator-metal (MIM) devices, which also show chemi-currents for many exothermic surface reactions.64-68... 

The LOFO approach, based on capillary interactions induced by liquid-solid interfaces, is used for transferring prefabricated thin solid metal films onto molecu-larly modified solid substrates. In spite of the fact that the glass/metal pad during the lift-off process leaves a relatively rough (1 nm) surface, several types of device have been fabricated by LOFO [154-156]. 

In SPR experiments -polarized light of a certain wavelength strikes the interface between the two media,71 72 which is coated with a thin metal film. The wave vector of the evanescent wave is given by the following equation 71... 

In actual experiments in biophysics, the interface may not be a simple interface between two media, but rather a stratified multilayer system. One example is the case of a biological membrane or lipid bilayer interposed between glass and aqueous media. Another example is a thin metal film coating, which quenches fluorescence within the first 10 nm of the surface... 

For a glass/metal film/water interface, this criterion is... 

E. H. Hellen and D. Axelrod, Fluorescence emission at dielectric and metal-film interfaces,... 

Most microhotplate-based chemical sensors have been realized as multi-chip solutions with separate transducer and electronics chips. One example includes a gas sensor based on a thin metal film [16]. Another example is a hybrid sensor system comprising a tin-oxide-coated microhotplate, an alcohol sensor, a humidity sensor and a corresponding ASIC chip (Application Specific Integrated Circuit) [17]. More recent developments include an interface-circuit chip for metal oxide gas sensors and the conccept for an on-chip driving circuitry architecture of a gas sensor array [18,19]. 

We examine an electron transfer of hydrated redox particles (outer-sphere electron transfer) on metal electrodes covered with a thick film, as shown in Fig. 8-41, with an electron-depleted space charge layer on the film side of the film/solution interface and an ohmic contact at the metal/film interface. It appears that no electron transfer may take place at electron levels in the band gap of the film, since the film is sufficiently thick. Instead, electron transfer takes place at electron levels in the conduction and valence bands of the film. 

Thus, in the stationary state, the rate of anodic transfer of metal ions across the metal/film interface equals the rate of anodic transfer of metal ions across the film/solution interface this rate of metal ion transfer represents the dissolution rate of the passive film. The thickness of the passive film at constant potential remains generally constant with time in the stationary state of dissolution, although the thickness of the film depends on the electrode potential and also on the dissolution current of the passive film. 

TMM handles thin metallic films as well, as they are used in lO-sensors based on surface-plasmon-polaritons (SPP). SPPs appear at the dielectric-metal interface for TM polarization, exclusively. The sensor principle is to have a waveguide mode and the SPP close to resonance, and screen the resonance vs. angle or vs. wavelength to detect refractive index changes of the cladding. Figure 4 shows the resonance of the absorption vs. the... 

This expression is independent of the film thickness. Thus, when one considers reflective monitoring of metal film etching, only at the interface between film and substrate will a change in reflectivity be observed due to the change in refractive index. Although this is extremely useful for end point detection one still must apply films of known thickness for cases in which etch rate information is desired. 

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