Purely quadratic dispersion of surface plasmon in Ag/Ni(111): the influence of electron confinement

Surface plasmon dispersion in nanoscale thin Ag films deposited onto the Ni(111) surface was investigated by angle‐resolved electron energy loss spectroscopy. We found that the dispersion curve contains only the quadratic term. The vanishing of the linear term was ascribed to the presence in the film of Ag 5sp‐related quantum well states. Screening effects enhanced by electron confinement in Ag quantum well states push the position of the centroid of the induced charge of the surface plasmon less inside the interface compared to other Ag systems, rendering null the linear coefficient of the dispersion curve. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of surface ζ‐potential and isoelectric point of carbon surfaces using tracer particle suspensions

Carbon materials are widely used in a range of applications from biomaterials to sensing and electronics. Many of these applications rely on the ability to control carbon/water interfacial properties, in particular, surface charge density. This work reports a study of the electrokinetic properties of amorphous carbon thin films as a function of pH and surface chemistry. Surface ζ‐potential (SZP) and isoelectric point were determined using the tracer particle method. Initially, the use of sulfonated and amine‐terminated latex bead suspensions as tracer particles for the determination of SZP of reference polymer surfaces was validated. The tracer particle method was then applied to the determination of SZP and isoelectric point of macroscopic carbon surfaces with different surface chemistry. Highly graphitic and sp³‐rich hydrogenated carbon surfaces were found to display negative SZP, as expected for hydrophobic surfaces. The isoelectric point of the most highly graphitic surface was found to be pH_iso = 3.7. Surface oxidation of these films resulted in a decrease of SZP at all pH values and in a downshift of pH_iso to values lower than 1.5, consistently with the presence of surface acidic groups arising from oxidation. Results indicate that the specific choice of acid/base chemistry for the tracer particles does not significantly affect either SZP or pH_iso determinations. These results show that the tracer particle method in combination with widely available latex beads as tracers can be applied for the determination of carbon SZP as a function of pH. Copyright © 2017 John Wiley & Sons, Ltd.     

Electronic properties of (3/2 × 3/2)-Na/Cu(1 1 1)

High-resolution electron energy loss spectroscopy was used to study the electronic properties of (3/2 × 3/2)-Na/Cu(1 1 1) at room temperature. Loss spectra showed two-well distinct losses at 114 and 180 meV assigned to not dispersive charge density waves. Mechanisms to explain their existence are proposed. Moreover, the expected 2D plasmon of the Na quantum well state was not observed. The strong influence of the underlying Cu substrate may be responsible for the absence of such mode.     

Photochemical functionalization of gallium nitride thin films with molecular and biomolecular layers

We demonstrate that photochemical functionalization can be used to functionalize and photopattern the surface of gallium nitride crystalline thin films with well-defined molecular and biomolecular layers. GaN(0001) surfaces exposed to a hydrogen plasma will react with organic molecules bearing an alkene (C=C) group when illuminated with 254 nm light. Using a bifunctional molecule with an alkene group at one end and a protected amine group at the other, this process can be used to link the alkene group to the surface, leaving the protected amine exposed. Using a simple contact mask, we demonstrate the ability to directly pattern the spatial distribution of these protected amine groups on the surface with a lateral resolution of <12 mum. After deprotection of the amines, single-stranded DNA oligonucleotides were linked to the surface using a bifunctional cross-linker. Measurements using fluorescently labeled complementary and noncomplementary sequences show that the DNA-modified GaN surfaces exhibit excellent selectivity, while repeated cycles of hybridization and denaturation in urea show good stability. These results demonstrate that photochemical functionalization can be used as an attractive starting point for interfacing molecular and biomolecular systems with GaN and other compound semiconductors.     

Covalent photochemical functionalization of amorphous carbon thin films for integrated real-time biosensing

Recent studies have demonstrated that carbon, in the form of diamond, can be functionalized with molecular and/or biomolecular species to yield interfaces exhibiting extremely high stability and selectivity in binding to target biomolecules in solution. However, diamond and most other crystalline forms of carbon involve high-temperature deposition or processing steps that restrict their ability to be integrated with other materials. Here, we demonstrate that photochemical functionalization of amorphous carbon films followed by covalent immobilization of DNA yields highly stable surfaces with excellent biomolecular recognition properties that can be used for real-time biological detection. Carbon films deposited onto substrates at 300 K were functionalized with organic alkenes bearing protected amine groups and characterized using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The functionalized carbon surfaces were covalently linked to DNA oligonucleotides. Measurements show very high selectivity for binding to the complementary sequence, and a high density of hybridizing DNA molecules. Samples repeatedly hybridized and denatured 25 times showed no significant degradation. The ability to use amorphous carbon films as a basis for real-time biosensing is demonstrated by coating quartz crystal microbalance (QCM) crystals with a thin carbon film and using this for covalent modification with DNA. Measurements of the resonance frequency show the ability to detect DNA hybridization in real time with a detection limit of <3% of a monolayer, with a high degree of reversibility. These results demonstrate that functionalized films of amorphous carbon can be used as a chemically stable platform for integrated biosensing using only room-temperature processing steps.     

Structure-related effects in the electronic properties of Fe80B20 alloys

The electronic properties of the amorphous and sintered Fe₈₀B₂₀ alloys have been studied by electron energy loss spectroscopy. A correlation among energy loss data and X-ray absorption near edge structures has been attempted.Structure-related effects in the electronic properties of Fe₈₀B₂₀ alloy have been found and discussed.     

Development of Patterns for Digital Image Correlation Measurements at Reduced Length Scales

Methods for patterning metal thin films at the microscale and nanoscale by applying the patterns to metallic and polymeric materials for use in shape and deformation measurements in a scanning electron microsope (SEM) or other high magnification imaging system are described. In one approach, thin films of metallic materials (e.g., Au, Ag, Cu, and Cr) are applied to a variety of substrates. The coated samples are then placed into a reaction vessel, where the specimens are heated and exposed to a nitrogen atmosphere saturated with selected volatile chemicals. This process results in nano-scale remodeling of the metallic films, thereby affording high contrast random patterns with different morphologies. In a second approach, thin films of metallic materials, including gold and silver, also have been applied using a simplified UV photolithographic method requiring a minimum amount of laboratory preparation. Using selected substrates, both methods have been used successfully to transfer patterns onto polymeric and metallic materials ranging from 50–500 nanometers with chemical vapor rearrangement and 2 to 20 microns with UV photolithography, providing a pattern that can be used with digital image correlation to quantify both the surface profile and also surface deformations at reduced length scales.     

High resolution electron energy loss measurements of Na/Cu(111) and H2O/Na/Cu(111): dependence of water reactivity as a function of Na coverage

Collective electronic excitations occurring in Na layers grown on Cu(111) and in H2O/Na/Cu(111) have been investigated at room temperature by high resolution electron energy loss spectroscopy. Loss spectra taken for a coverage between 0.55 and 0.70 ML of Na are characterized by a feature at 3.0 eV assigned to a Mie resonance. Further increasing the Na coverage leads to the appearance of the Na surface plasmon at 3.9 eV. Water molecules dissociate on Na layers as shown by the appearance of the OH-Na vibration. Upon water adsorption, relevant effects on both electronic excitations and vibrational modes were observed as a function of Na coverage.     

In situ studies of the adsorption kinetics of 4-nitrobenzenediazonium salt on gold

Self-assembled organic layers are an important tool for modifying surfaces in a range of applications in materials science. Covalent modification of metal surfaces with aryldiazonium cations has attracted much attention primarily because this reaction offers a route for spontaneously grafting a variety of aromatic moieties from solution with high yield. We have investigated the kinetics of this process by performing real-time, in situ nanogravimetric measurements. The spontaneous grafting of 4-nitrobenzene diazonium salts onto gold electrodes was studied via quartz crystal microbalance (QCM) from aqueous solutions of the salt at varying concentrations. The concentration dependence of the grafting rate within the first 10 min is best modeled by assuming a reversible adsorption process with free energy comparable to that reported for arylthiols self-assembled on gold. Multilayer formation was observed after extended grafting times and was found to be favored by increasing bulk concentrations of the diazonium salt. Modified gold surfaces were characterized ex situ with cyclic voltammetry, infrared reflection absorbance spectroscopy, and X-ray photoemission spectroscopy. Based on the experimentally determined free energy of adsorption and on the observed grafting rates, we discuss a proposed mechanism for aryldiazonium chemisorption.     

Surface extended energy loss fine structures above the K-edge of oxygen on Al

Surface Extended Energy Loss Fine Structures (SEELFS) have been detected above the K-edge of oxygen adsorbed on an Al sample. This is the first evidence that the local geometry of adsorbates on metal surfaces can be investigated with the electron energy loss technique in the reflection mode. This experimental technique is highly surface sensitive and accurate bond lengths can be obtained. The oxidation model implied by our results for the OAl system is in agreement with data in the literature.