Dynamics of GDOES-induced surface roughening in metal interfaces

The roughness induced during glow-discharge optical-emission spectroscopy (GDOES) measurements has been reported to cause a loss of resolution during GDOES depth-profiling analysis. In this paper, we undertake for the first time a study of the dynamics of the surface morphology of chromium and titanium thin films (designed in mono and multilayer structures) under the impinging of GDOES incoming ions. We performed this study under the theoretical framework of the dynamic scaling theory, by analysing surface morphology changes, as measured ex-situ by AFM, with irradiation time. For single metal layers it was found that, after an initial surface smoothening, the surface undergoes a rapid steep roughening for both systems, with quite similar quantitative dynamics. Once this roughening ends a second temporal scaling regime arises, operating for long length scales with dynamics depending on the sputtering rate of the material. For the chromium layer, with a very high sputtering rate of 5.5 μm min^?1, this regime is consistent with the KPZ model, whereas for the titanium layer an EW scaling regime is indicated. These different scaling regimes are consistent with the development of larger surface slopes for the Cr system. In the multilayer systems, the initial roughness induced on the top Cr layer by GDOES has similar dynamics to that for single-layer Cr. However, a clear decrease in the roughness was observed once the underlying Ti layer, with a lower sputtering rate, was reached. This decrease in the induced roughness is maintained while the Ti layer is eroded. Therefore, choice of appropriate material (i.e. sputtering yield values) combinations and of their depth of location can enable tuning of GDOES-induced roughness and achieve substantial control over the depth profiling process.     

Experimental demonstration of surface selection rules for SERS on flat metallic surfaces

We have measured the polarization and incident angle dependence of the Surface-Enhanced Raman Scattering (SERS) signal of a nile blue monolayer adsorbed on a flat gold surface. Comparisons with predictions of electromagnetic (EM) theory indicate that the molecules are predominantly adsorbed flat on the surface. These results provide the most direct demonstration of the concept of surface selection rules in SERS, and further confirm the validity of the SERS-EM model beyond the |E|(4)-approximation.     

Energy level alignment at organic semiconductor/metal interfaces: effect of polar self-assembled monolayers at the interface

We determined the shifts in the energy levels of approximately 15 nm thick poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] films deposited on various substrates including self-assembled monolayer (SAM) modified Au surfaces using photoelectron spectroscopy. As the unmodified substrates included Au, indium tin oxide, Si (with native oxide), and Al (with native oxide), a systematic shift in the detected energy levels of the organic semiconductor was observed to follow the work function values of the substrates. Furthermore, we used polar SAMs to alter the work function of the Au substrates. This suggests the opportunity to control the energy level positions of the organic semiconductor with respect to the electrode Fermi level. Photoelectron spectroscopy results showed that, by introducing SAMs on the Au surface, we successfully increased and decreased the effective work function of Au surface. We found that in this case, the change in the effective work function of the metal surface was not reflected as a shift in the energy levels of the organic semiconductor, as opposed to the results achieved with different substrate materials. Our study showed that when a substrate is modified by SAMs (or similarly by any adsorbed molecules), a new effective work function value is achieved; however, it does not necessarily imply that the new modified surface will behave similar to a different metal where the work function is equal to the effective work function of the modified surface. Various models and their possible contribution to this result are discussed.     

Characterization of the interface dipole at organic/ metal interfaces

In organics-based (opto)electronic devices, the interface dipoles formed at the organic/metal interfaces play a key role in determining the barrier for charge (hole or electron) injection between the metal electrodes and the active organic layers. The origin of this dipole is rationalized here from the results of a joint experimental and theoretical study based on the interaction between acrylonitrile, a pi-conjugated molecule, and transition metal surfaces (Cu, Ni, and Fe). The adsorption of acrylonitrile on these surfaces is investigated experimentally by photoelectron spectroscopies, while quantum mechanical methods based on density functional theory are used to study the systems theoretically. It appears that the interface dipole formed at an organic/metal interface can be divided into two contributions: (i) the first corresponds to the "chemical" dipole induced by a partial charge transfer between the organic layers and the metal upon chemisorption of the organic molecules on the metal surface, and (ii) the second relates to the change in metal surface dipole because of the modification of the metal electron density tail that is induced by the presence of the adsorbed organic molecules. Our analysis shows that the charge injection barrier in devices can be tuned by modulating various parameters: the chemical potential of the bare metal (given by its work function), the metal surface dipole, and the ionization potential and electron affinity of the organic layer.     

Oscillatory electrodeposition of metal films at liquid/liquid interfaces induced by the large surface energy of growing deposits

Electrodeposition of zinc (Zn) at an aqueous ZnSO4/n-butylacetate (BuAc) interface (liquid/liquid (LL) interface) showed a potential oscillation in the region of the current density exceeding the diffusion-limited one, accompanied by formation of two-dimensional Zn film with a concentric pattern at the LL interface. In-situ optical microscopic inspections revealed that the oscillatory growth of the Zn film synchronized with meniscus oscillation of the LL interface. The vigorous growth of the deposits occurs only when the shape of the meniscus becomes hollow on the negative potential side of the potential oscillation. On the other hand, on the positive side, the meniscus becomes almost flat and the deposits formed in the preceding stage are thickened. A mechanism is proposed to explain the oscillatory Zn electrodeposition coupled with the meniscus oscillation, on the basis of the fact that the interfacial tension at the growing metal/aqueous solution interface is extremely large.     

Optical spectroscopy for in situ characterisation of semiconductor interfaces and layers

The potential of optical techniques for semiconductor interfaces and growing layers is demonstrated using in particular the example of Raman spectroscopy in combination with molecular beam epitaxial (MBE) growth. Recent developments allow this method to be applied not only in situ but while growth progresses. This application critically depends on the resonant excitation which provides the required sensitivity for layers in the nanometre range. Here the heteroepitaxy of II–VI compound semiconductors on III–V substrates serves as an example to illustrate the wealth of information, e.g. on layer composition, crystallinity, growth rate, and interfacial reactivity. Very recent results on gallium nitride growth clearly reveal that such experiments can be performed even at temperatures as high as 685?°C.     

Effect of molecular binding to a semiconductor on metal/molecule/semiconductor junction behavior

Diodes made by (indirectly) evaporating Au on a monolayer of molecules that are adsorbed chemically onto GaAs, via either disulfide or dicarboxylate groups, show roughly linear but opposite dependence of their effective barrier height on the dipole moment of the molecules. We explain this by Au-molecule (electrical) interactions not only with the exposed end groups of the molecule but also with its binding groups. We arrive at this conclusion by characterizing the interface by in situ UPS-XPS, ex situ XPS, TOF-SIMS, and Kelvin probe measurements, by scanning microscopy of the surfaces, and by current-voltage measurements of the devices. While there is a very limited interaction of Au with the dicarboxylic binding groups, there is a much stronger interaction with the disulfide groups. We suggest that these very different interactions lead to different (growth) morphologies of the evaporated gold layer, resulting in opposite effects of the molecular dipole on the junction barrier height.     

Spectromicroscopy and internal photoemission spectroscopy of semiconductor interfaces

For decades, techniques based on synchrotron light sources have played a central role in solid interface research. This role has been recently enhanced by two factors: the commissioning of the third generation of sources, characterized by unprecedented levels of brightness, and the first utilization cases of another class of photon sources related to synchrotron facilities, the free electron lasers (FEL's). This review will first present some relevant examples of how the new facilities are changing the scene of interface research, most notably in the domain of spectromicroscopy. We will specifically illustrate how the crucial problem of the lateral fluctuations of interface properties is being attacked with both synchrotron-light and FEL techniques. Then, we will argue that the present applications are only marginally exploiting the amazing capabilities of the new sources. The main case to illustrate this point is coherence-sharpened x-ray imaging, a very promising and spectacular technique developed for medical radiology, which could find extremely interesting applications in interface research.     

Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study

An analysis of surface potential nonlinearity (ψ₀) at metal oxide/electrolyte interfaces is presented. By using grand canonical Monte Carlo simulations of a simple lattice model of an interface, we show that a correlation exists between ionic strength, as well as surface site densities, and the non-Nernstian response of a metal-oxide electrode. We propose two approaches to deal with the ψ₀-nonlinearity: one based on perturbative expansion of the Gibbs free energy and another based on the assumption of the pH dependence of surface potential slope. The theoretical analysis based on our new potential form gives excellent performance in extreme pH regions, where classical formulae for ψ₀ are unjustified. The new formula is general and independent of any underlying assumptions. For this reason, it can be directly applied to experimental surface potential measurements, including those for individual surfaces of single crystals, as we present for data reported by Kallay and Preo?anin [6].     

Plasmonic metal/semiconductor hybrid nanomaterials for solar to chemical energy conversion

Plasmonic nanomaterials are sources of light,heat and electrons at nanometer scale.Given the outstand-ing performance in harvesting and converting solar energy ...     

Metal/insulator/metal junctions for electrochemical surface science

We describe the preparation and characterization of Al-AlO_x-Ag tunnel junctions and calculate the energy distribution of the tunneling hot electrons in the range 0–2.5 eV above the Fermi level of silver. Because the mean free path of the hot electrons is of the order of the thickness of the silver film of the junction, which is at the same time the electrode in contact with an electrolyte, new surface effects can be studied. Hot electrons can be injected into the nonhydrated electron band in water. Hot electrons also cause hydrogen evolution at electrode potentials more positive than the ones needed in common electrochemistry. We observed the emission of hot electrons into silver during transients of hydrogen oxidation at silver and during oxidation of overpotential hydrogen on platinum clusters deposited on the silver electrode. The tunnel current at constant tunnel voltage can be changed by faradaic reactions, but surprisingly also by nonfaradaic reactions; this is assigned to a mesoscopic quantum phenomenon.     

Engineering large-scaled electrochromic semiconductor films as reproductive SERS substrates for operando investigation at the solid/liquid interfaces

Although surface-enhanced Raman spectroscopy (SERS) has been applied for gathering fingerprint information, even in single molecule analysis, the decayed Raman signals in aqueous solutions largely obstruct the on-site insight reaction process. In this study, large-scaled semiconductor films with multi-walled (TiO₂/WO₃/TiO₂) nanopore distribution are fabricated by combining electrochemical anodization and sputtering technique, and then employed as the SERS substrates for detection of molecules at the solid/liquid interfaces. Given the remarkably improved electrochromic property of the multi-walled film, such SERS substrates were endowed with tunable oxygen vacancy (V_O) density and distribution via simply applying electrochemical bias voltage, which enabled one to achieve an enhanced charge transfer efficiency and thus a remarkably increased Raman signal even in solution. The V_O-rich SERS substrate is highly repeatable, thus providing a reliable platform for in-situ monitoring of the target molecules or intermediates at the solid/liquid interfaces.     

Energy level alignment at metal/organic semiconductor interfaces: "pillow" effect, induced density of interface states, and charge neutrality level

A unified model, embodying the "pillow" effect and the induced density of interface states (IDIS) model, is presented for describing the level alignment at a metal/organic interface. The pillow effect, which originates from the orthogonalization of the metal and organic wave functions, is calculated using a many-body linear combination of atomic orbitals Hamiltonian, whereby electron long-range interactions are obtained using an expansion in the metal/organic wave function overlap, while the electronic charge of both materials remains unchanged. This approach yields the pillow dipole and represents the first effect induced by the metal/organic interaction, resulting in a reduction of the metal work function. In a second step, we consider how charge is transferred between the metal and the organic material by means of the IDIS model: Charge transfer is determined by the relative position of the metal work function (corrected by the pillow effect) and the organic charge neutrality level, as well as by an interface parameter S, which measures how this potential difference is screened. In our approach, we show that the combined IDIS-pillow effects can be described in terms of the original IDIS alignment corrected by a screened pillow dipole. For the organic materials considered in this paper, we see that the IDIS dipole already represents most of the realignment induced at the metal/organic interface. We therefore conclude that the pillow effect yields minor corrections to the IDIS model.     

Photoelectron spectroscopy of electronic surface structure of the Cs/GaN and Cs/InN interfaces

The electronic structure of the epitaxial GaN, InN nanolayers, and the ultrathin Cs/GaN and Cs/InN interfaces was investigated under ultrahigh vacuum at various Cs coverages. The experiment was carried out using synchrotron-based photoelectron spectroscopy. The photoemission spectra of the valence band and the In 4d, N 2s, Ga 3d, and Cs 4d semicore levels were studied as a function of Cs coverages. It was found that the Cs adsorption in the submonolayer coverage region causes substantial changes in the spectra due to charge transfer between the Cs adlayer and surface Ga or In atoms. The strong interaction of the dangling bonds of Ga or In with Cs adatoms effectively increases the Ga or In valency.     

Electrochemical impedance simulation of a metal oxide heterostructure/electrolyte interface: A review

The results of an analysis of the literature data obtained when investigating processes of charge transfer at interfaces of heterostructures formed by various methods, including the high-energy methods, are presented in this paper. The performed investigation of oxide layers at the titanium surface, with use made of impedance spectroscopy data made it possible to reveal the nature and influence of some processes and factors on the charge transfer mechanism realized at a metal oxide heterostructure/electrolyte interface. Simulating an oxide/electrolyte interface gives one a chance to identify, in a spectrum, the responses that characterize the behavior of porous and poreless layers, as well as the responses that are due to the space-charge region formed in the oxide material and to the corrosion and diffusion processes.     

Electron-stimulated oxidation of metal and semiconductor surfaces

The electron-stimulated adsorption of oxygen from the gas phase is studied. The basic laws governing the changes in the surface structure induced by electron-stimulated adsorption are determined.     

Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface

A critical factor limiting the rates of photocatalytic reactions, including water splitting, on oxide semiconductors is the high rate of charge-carrier recombination. In this contribution, we demonstrate that this issue can be alleviated significantly by combining a semiconductor photocatalyst with tailored plasmonic-metal nanostructures. Plasmonic nanostructures support the formation of resonant surface plasmons in response to a photon flux, localizing electromagnetic energy close to their surfaces. We present evidence that the interaction of localized electric fields with the neighboring semiconductor allows for the selective formation of electron/hole (e(-)/h(+)) pairs in the near-surface region of the semiconductor. The advantage of the formation of e(-)/h(+) pairs near the semiconductor surface is that these charge carriers are readily separated from each other and easily migrate to the surface, where they can perform photocatalytic transformations.     

Some aspects of discreteness-of-charge and ion-size effects for ions adsorbed at charged metal/aqueous electrolyte interfaces

It is argued that the self-image potential of an ion adsorbed on a charged metal from an aqueous electrolyte is described in terms of multiple imaging and not single imaging in the metal as proposed by Bockris. The image potential of an isolated ion situated on the i.H.p. in the inner region with a continuously and smoothly varying dielectric profile is calculated. This is compared with the corresponding potential for an inner region model with a discontinuous dielectric profile. It is shown that when the position of the i.H.p. relative to the o.H.p. is changed, the two potentials will in general cross each other such that the discontinuous model has the more negative self-image potential when the i.H.p. approaches the o.H.p. The scaled-particle expression for the entropic contribution due to ion-size effects in the adsorption isotherm of an ion in the inner region is compared with the corresponding Flory-Huggins formula. It is demonstrated that the two theories can give very different results. In particular, when the adsorbed ions are considerably larger than the solvent molecules, it is possible that scaled-particle theory leads to a ‘negative’ ion-size entropy term, which decreases with increase in density of adsorbed ion.