Desorption of metal atoms with laser light of different polarization

Laser-induced desorption of metal atoms from the surface of small metal particles has been investigated as a function of the shape of the particles and the polarization of the incident laser light. The particles were supported on LiF, quartz or sapphire substrates. In a first set of experiments, the shape of the particles was determined by recording optical transmission spectra with s- and p-polarized light incident under an angle of typically 40° with respect to the surface normal. The metal particles turn out to be oblate, the ratio of the axes perpendicular and parallel to the substrate surface being on the order of 0.5. This ratio decreases with increasing particle size. Also, the particles change shape if the temperature is raised. In further experiments, s- and p-polarized light has been used to stimulate desorption of atoms via surface plasmon excitation. It is found that the desorption rate markedly depends on the polarization of the light. This is explained by excitation of the collective electron oscillation along different axes of the non-spherical particles.     

Direct visual evidence for the chemical mechanism of surface‐enhanced resonance Raman scattering via charge transfer

We describe the chemical and electromagnetic enhancements of surface‐enhanced resonance Raman scattering (SERRS) for the pyridine molecule absorbed on silver clusters, in which different incident wavelength regions are dominated by different enhancement mechanisms. Through visualization we theoretically investigate the charge transfer (CT) between the molecule and the metal cluster, and the charge redistribution (CR) within the metal on the electronic intracluster collective oscillation excitation (EICOE). The CT between the metal and the molecule in the molecule–metal complex is considered as an evidence for chemical enhancement to SERRS. CR within the metal on EICOE is considered as an evidence for the electromagnetic enhancement by collective plasmons. For the incident wavelength from 300 to 1000 nm, the visualized method of charge difference density can classify the different wavelength regions for chemical and electromagnetic enhancement, which are consistent with the formal fragmented experimental studies. Copyright © 2008 John Wiley & Sons, Ltd.     

分子激发中的表面等离激元增强效应

金属纳米粒子的表面等离激元增强效应是纳米科学领域的一个研究热点.针对染料分子与金属纳米粒子的耦合系统,应用偶极-偶极近似计算分子与金属纳米粒子的库仑相互作用,并应用密度矩阵理论描述在不同极化方向的电场作用下的电荷输运过程,分析了分子与金属纳米粒子在不同相对位置下分子激发态的动力学过程,发现表面等离激元的增强效应与分子和金属钠米粒子的相对位置以及等离激元的耗散系数有密切关系,详细讨论了分子与金属纳米粒子间的耦合强度、外场的极化方向、等离激元的寿命及共振激发条件对分子激发态及表面等离激元增强的影响,分析了分子-金属纳米粒子耦合系统中表面等离激元增强效应的物理本质.     

Use of laser beams for vaporizing materials in spectral analysis

It is shown that approximately 20% of the light energy of a laser beam incident on copper-zinc alloys is expended in the liberation and excitation of the alloy atoms. The remaining portion of the beam energy is lost in reflection from the metal surface. The fraction of energy reflected corresponds to the reflection coefficient of the metal.     

Trinal Nature of the Excitation of Bulk Plasmons by a Fast Charged Particle at Grazing Incidence on the Interface between Vacuum and a Metal with Strong Spatial Dispersion

The excitation and propagation of bulk and surface (surface waves of transition radiation of plasmons at frequencies above the plasma frequency) plasma waves by incident electrons moving both in vacuum toward the surface of a metal and inside the metal whose boundary elastically and spectacularly reflects internal nonequilibrium electrons have been analyzed. In contrast to work [B. N. Libenson, J. Exp. Theor. Phys. 113, 553 (2011)], attention in this work is focused on the influence of surface effects on bulk-plasmon excitation by incident electrons. The probabilities and spectra of single characteristic energy loss of an intermediate- energy electron (50–500 eV) moving at an angle to the surface of the medium in three regions: in vacuum, in the medium, and again in vacuum after the electron leaves the medium are calculated. The kinetic approximation is used for the dielectric function, where the entire range of the plasmon spectrum is taken into account correctly for the problem under consideration. In the indicated energy range of incident electrons, surface effects, on the one hand, significantly reduces the probability of excitation of bulk plasma waves in the medium with strong spatial dispersion, in particular, as compared to the results obtained in [B.N. Libenson, J. Exp. Theor. Phys. 113, 553 (2011)], where surface effects were disregarded and the probability of bulkplasmon excitation by a 200-eV electron incident and emitted perpendicularly to the boundary is about one third of that in the unbounded medium. On the other hand, at grazing incidence from vacuum, the probability of transition radiation of bulk plasmons increases significantly and can lead to a change in the character of the angular dependence of the intensity of bulk plasma energy loss. Thus, the main result of this work is that a decrease in the glancing angle of the fast electron with respect to the vacuum–metal interface is accompanied both by an increase in the contribution from the transition mechanism to the probability of bulk-plasmon excitation in the vacuum region and by a decrease in the contribution from Cherenkov and bremsstrahlung mechanisms of excitation in the medium. The probability of bulk-plasmon excitation in the vacuum region exceeds the probability of excitation at the further motion of the electron in metallic aluminum at angles of incidence larger than 65°, 70°, and 75° at the energies E = 200, 350, and 500 eV, respectively.     

Surface plasmon-polaritons wave fields in the vicinity of a metallic nanohole

It is shown that metal surface with a nanohole can support surface plasmon-polaritons (SPP), whose wave fields are described by Hankel functions. These plasmons can be excited by an electromagnetic wave incident at the metal surface. The optical transmission through subwavelength holes in metal films can essentially be enhanced by interaction of the incident light with surface plasmons. Dependence of excitation of the wave field of SPP on the incidence angle and on the wavelength of incident light is considered.     

Charge transfer effects in surface enhanced Raman scattering

Surface enhanced Raman scattering (SERS) due to charge transfer interactions between the adsorbed molecule and the metal surface is analyzed using the semiempirical Wolfsberg-Helmholz method¹ to relate the molecule-surface interactions and the resulting charge transfer states to the overlap integrals between the metal conduction-band orbitals and an acceptor or donor molecular orbital of the molecule. Calculations for the model system of ethylene adsorbed on silver (approximated as a simple cubic metal with tight binding wave functions constructed from Ag 5s valence orbitals), with charge-transfer excitation of an electron from the metal to the antibonding ethylene π orbital, show that charge-transfer Raman enhancements of the order of 10 to 1000 are possible if the charge-transfer band is partially resonant with the exciting radiation. The net enhancement is the product of the charge-transfer gain and the electrodynamic enhancement due to plasmon resonances at surface roughness elements. Symmetric vibrations usually will be enhanced substantially more than nonsymmetric ones by charge-transfer because, in contrast to non-resonant Raman scattering, the vibrational coupling is primarily Franck- Condon (due to differences in the equilibrium nuclear configurations of the ground and excited charge transfer states and the resulting nonorthogonality of different vibrational sublevels of these states) rather than Herzberg-Teller (due to vibrationally induced changes in the electronic wave functions). The charge-transfer mechanism is selective with the most enhanced vibrations involving those atoms which experience the greatest change in electron density between the ground and excited charge-transfer state. A recent report of SERS for benzene on platinum,² strongly suggests charge-transfer enhancement because the electromagnetic-field-enhancing plasmon resonances are strongly damped in this metal.The complete paper will be published in the December 1, 1982 issue of the Journal of Chemical Physics.     

Interactions of incident H atoms with metal surfaces

Atomic hydrogen is a highly reactive species of interest because of its role in a wide range of applications and technologies. Knowledge about the interactions of incident H atoms on metal surfaces is important for our understanding of many processes such as those occurring in plasma-enhanced catalysis and nuclear fusion in tokamak reactors. Herein we review some of the numerous experimental surface science studies that have focused on the interactions of H atoms that are incident on low-Miller index metal single-crystal surfaces. We briefly summarize the different incident H atom reaction mechanisms and several of the available methods to create H atoms in UHV environments before addressing the key thermodynamic and kinetic data available on metal and modified metal surfaces. Generally, H atoms are very reactive and exhibit high sticking coefficients even on metals where H₂ molecules do not dissociate under UHV conditions. This reactivity is often reduced by adsorbates on the surface, which also create new reaction pathways. Abstraction of surface-bound D(H) adatoms by incident H(D) atoms often occurs by an Eley-Rideal mechanism, while a hot atom mechanism produces structural effects in the abstraction rates and forms homonuclear products. Additionally, incident H atoms can often induce surface reconstructions and populate subsurface and bulk absorption sites. The absorbed H atoms recombine to desorb H₂ at lower temperature and can also exhibit higher subsequent reactivity with adsorbates than surface-bound H adatoms. Incident H atoms, either directly or via sorbed hydrogen species, hydrogenate adsorbed hydrocarbons, sulfur, alkali metals, oxygen, halogens, and other adatoms and small molecules. Thus, H atoms from the gas phase incident on surfaces and adsorbed layers create new reaction channels and products beyond those found from interactions of H₂ molecules. Detailed aspects of the dynamics and energy transfer associated with these interactions and the important applications of hydrogen in plasma processing of semiconductors are beyond the scope of this review.     

Surface molecules and chemisorption: I. Adatom density of states

A useful picture of chemisorption on metal surfaces is one in which a localized molecule is formed between the adatom and its nearest neighbor substrate atoms. The interaction responsible for the molecule formation is treated as the coupling between the adsorbate state and a group orbital formed from a linear combination of atomic orbitals on the substrate atoms. Within the surface molecule picture, level width and level shift functions, given by Newns modification of the Anderson theory, have been calculated and the resulting adatom density of states function has been obtained. This has been done for model systems in which the substrate is either a free electron metal or a tightbinding p-band metal and the adsorbate is s or p like. The results show how it is possible to simultaneously have narrow virtual levels due to chemisorption (～ 1 eV) which previously implied weak interactions and also high binding energies (? 3 eV) as are observed experimentally.     

Electron-stimulated desorption of rare-earth metal atoms

The yield of europium and samarium atoms in electron-stimulated desorption from layers of rare-earth metals (REMs) adsorbed on the surface of oxidized tungsten has been measured as a function of the incident electron energy, surface coverage by REMs, degree of tungsten oxidation, and substrate temperature. The measurements were performed using the time-of-flight method with a surface-ionization-based detector within the substrate temperature interval 140–600 K. The yield studied as a function of electron energy has a resonance character. Overlapping resonance peaks of Sm atoms are observed at electron energies of 34 and 46 eV, and those of Eu atoms, at 36 and 41 eV. These energies correlate well with the REM 5p and 5s core-level excitation energies. The REM yield is a complex function of the REM coverage and substrate temperature. The peaks due to REM atoms are seen at low REM coverages only, and their intensity usually passes through a maximum with increasing coverage and substrate temperature. The concentration dependence of the REM atom yield is affected by the deposition of slow Ba⁺ ions, but only if they are deposited after the REM adsorption. At higher REM coverages, additional peaks are observed at electron energies of 42, 54, and 84 eV, which originate from excitation of the 5p and 5s tungsten levels and result from desorption of SmO and EuO molecules. The temperature dependence of the intensity of these peaks is explained to be due to the order-disorder phase transition. The desorption of REM atoms is the result of their reversed motion through the adsorbed REM layer, and the SmO and EuO molecules desorb due to the formation of an antibonding state between the REM oxide molecules and the tungsten ions.     

Visible transmission through metal-coated colloidal crystals

Large-scale periodically structured metal films with enhanced optical transmission in visible frequencies were fabricated by depositing silver onto colloidal crystals. The obtained transmission properties are similar to those observed through periodical hole arrays in planar metal films. We have experimentally observed two enhanced transmission pass bands in visible frequencies in these metal films due to the excitation of surface plasmon polaritons. The peak positions of the pass bands depend on the size of the colloidal spheres. The transmission spectra highly depend on the incident angle for p-polarized light but are weak for s-polarized light. Our fabrication method provides a promising approach for the fabrication of large-scale low-cost plasmonic crystals with submicrometer periodicity.     

Effect of secondary electrons on the yield of electron-stimulated desorption of neutral atoms under differently localized core-level excitations in a substrate

This paper reports on the results of a comparative analysis of the changes in the electron-stimulated desorption (ESD) yield of neutral particles from layers of alkali metal and Ba atoms deposited on the surface of a metal atop an oxygen (O/W, O/Mo) or germanium (Ge/W) film as a function of the incident electron beam energy E. The atomic yield q(E) is compared with the ionization cross sections of the core levels whose ionization potentials coincide with the ESD yield thresholds of the atoms. Three types of dependences q(E) are discussed, and the role of the secondary electrons generated in the electron-bombarded substrate for each type of the dependence of the ESD yield on E is elucidated. The analysis is based on the experimental studies performed by the authors in the recent years, starting from 1991. It is shown that the actual type of dependence q(E) is determined both by the actual localization of the atom excited by the electron beam and by the extent of localization of the core excitation resulting in ESD.     

Optical second-harmonic generation by supported metal clusters: Size and shape effects

Optical Second Harmonic Generation (SHG) by metal clusters has been investigated. For this purpose clusters were generated by the deposition and nucleation of metal atoms on a LiF(100) single crystal surface under ultrahigh vacuum conditions. The size and shape of the metal particles was characterized by optical transmission spectroscopy. The SHG intensity was detected in situ as a function of cluster size during the nucleation. Fundamental wavelengths of =1064 and 532 nm were used and the SHG signal was measured for different polarization combinations of the incident and registered light. SH radiation is detectable for particles as small as approximately 1 nm. The signal grows monotonically as a function of particle size, passes a maximum and finally drops off. This behavior is discussed in terms of resonant enhancement of the signal by surface plasmon excitation and changes of ⁽²⁾ as a function of particle size and shape. In further experiments the chemisorption of oxygen on the surface of the metal particles was studied. The SH signal decreases as a function of oxygen coverage and amounts to only about 15% of the initial value upon chemisorption of one monolayer. This indicates that the SH signal originates almost exclusively from the surface of the clean clusters and that higher order bulk contributions are negligible.     

Excitation and emission of metal electrons in atom-surface collisions

Electron-hole pair excitation and ionization probabilities are calculated for atomic collisions with metal surfaces at high incident energies. The method adopted is based on a Sudden Collision Approximation, and a realistic model is employed for the bound and continuum electronic states involved. The parameters used in the calculations are for Ar, He, H atoms impinging on a Li surface at 300 eV. The main results are: (1) Only single electron-hole pair excitations are important; multiple pair contributions are small. (2) The transitions are dominated by the behavior of the electronic wavefunctions in the tunneling region and may serve as a probe of this regime. (3) The excitation efficiency is in the order H ? Ar ? He, the effectiveness of hydrogen being due to its stronger, longer-range coupling. (4) The maximum excitation probabilities are for electrons ejected with relatively low excess energies. (5) Total transition probabilities are about 0.5 per collision for H, and about 0.1 for Ar, indicating that these are important, easily detectable processes. Experiments in this field should provide important information on electronic wavefunctions at the metal-gas interface, and on gas-metal interactions at high energies.     

Extraordinary optical transmission through metal gratings with single and double grooved surfaces

We investigate the transmission properties of a normally incident TM plane wave through metal films with periodic parabolic-shaped grooves on single and double surfaces using the finite-difference-time-domain method. Nearly zero transmission efficiency is found at wavelengths corresponding to surface plasmon excitation on a flat surface in the case where the single surface is grooved. Meanwhile, resonant excitation of surface plasmon polariton (SPP) Bloch modes leads to a strong transmission peak at slightly larger wavelengths. When the grating is grooved on double surfaces, the transmission enhancement can be dramatically improved due to the resonant tunnelling between SPP Bloch modes.     

Pulse regime in formation of fractal fibers

The pulse regime of vaporization of a bulk metal located in a buffer gas is analyzed as a method of generation of metal atoms under the action of a plasma torch or a laser beam. Subsequently these atoms are transformed into solid nanoclusters, fractal aggregates and then into fractal fibers if the growth process proceeds in an external electric field. We are guided by metals in which transitions between s and d-electrons of their atoms are possible, since these metals are used as catalysts and filters in interaction with gas flows. The resistance of metal fractal structures to a gas flow is evaluated that allows one to find optimal parameters of a fractal structure for gas flow propagation through it. The thermal regime of interaction between a plasma pulse or a laser beam and a metal surface is analyzed. It is shown that the basic energy from an external source is consumed on a bulk metal heating, and the efficiency of atom evaporation from the metal surface, that is the ratio of energy fluxes for vaporization and heating, is 10^–3–10^–4 for transient metals under consideration. A typical energy flux (~10⁶ W/cm²), a typical surface temperature (~3000 K), and a typical pulse duration (~1 μs) provide a sufficient amount of evaporated atoms to generate fractal fibers such that each molecule of a gas flow collides with the skeleton of fractal fibers many times.     

CO adsorption on Rh, Pd and Ag atoms deposited on the MgO surface: a comparative ab initio study

The adsorption properties of CO molecules adsorbed on Rh, Pd, and Ag atoms supported on various sites of the MgO surface have been studied by means of a density functional cluster model approach. The metal atoms are stabilized with different binding energies on the regular and morphological defect sites of the surface. Among others we considered oxide anions, neutral and charged anion vacancies (F centers) located at terraces, steps, edges, and corners. CO is used as a probe molecule to characterize where the metal atoms are located. This is done by analyzing how the metal-CO binding energy and the C-O stretching frequency change as function of the substrate site where the metal atom is bound.     

Surface-plasmon-assisted electromagnetic field enhancement in semiconductor quantum dots

The temporal development of incident electromagnetic plane waves across semiconductor quantum dots (QDs) is analyzed by the finite-difference time-domain method. By coating the QDs using thin metal films, surface plasmon polaritons (SPPs) can be created. As illustration, our modeling approach is applied to fluorescent multiphoton quantum dots made of cadmium sulphide of particular size (3.7 nm) and energy band gap (2.67 eV). When such a QD is coated by a metal film, a dipole-formed SPP is generated at the external surface of the coated QD by the incident electromagnetic wave with a photon energy of 1.34 eV corresponding to a two-photon process. When the thickness of the metal film is 0.37 nm, the peak intensity of the SPP oscillates through both the thin metal film and the core QD, resulting in an electromagnetic field inside the QD enhanced by a factor of 10, and thus an increased two-photon excitation that can be useful for bioimaging applications. Further increasing the metal film thickness blockades the SPP initially generated at the external surface of the coated QD from penetrating through the metal film, reducing the electromagnetic field inside the QD. PACS 73.22.-f; 78.67.Hc     

Does the excitation of a plasmon resonance induce a strong chemical enhancement in SERS? On the relation between chemical interface damping and chemical enhancement in SERS

In this contribution, a fundamental new approach is made to explain high enhancement factors in surface-enhanced Raman spectroscopy (SERS) on the basis of chemical enhancement. Usually, high SERS enhancement factors are explained by electromagnetic enhancements due to the excitation of localized surface plasmon resonances and strong near field dipole–dipole coupling. However, very often the corresponding SERS spectra show clear signatures of a chemical enhancement. I propose that this contradiction is easily solved by taking chemical interface damping of the plasmon resonance into account. Chemical interface damping is caused by an electron transfer from the metallic structure into an adsorbate. However, this mechanism is also the basis for chemical enhancement in SERS, i.e., an electron transfers in the lowest unoccupied molecular orbital of the molecule and back to the metal. Hence, if a molecule causes a strong chemical interface damping, the excitation of plasmons is still the key factor for the SERS enhancement. But the reason for this enhancement might be not solely due to electromagnetic fields rather than by a chemical enhancement due to electron transfers from the metal to the molecules.