Where do the counterions go? Tip-induced dissociation of self-assembled triazatriangulenium-based molecules on Au(111).

Chemical coupling of functional molecules on top of the so-called platform molecules allows the formation of functional self-assembled monolayers (SAMs). An often-used example of such a platform is triazatriangulenium (TATA), which features an extended aromatic core providing good electronic contact to the underlying metal surface. Here, we present a study of the SAM formation of a TATA platform on Au(111) employing scanning tunneling microscopy (STM) under ambient atmospheric conditions. In solution, the TATA platform is stabilized by BF4 counterions, while after deposition on a gold substrate, the localization of the BF4 counterions remains unknown. We used 1,2,4-trichlorobenzene as a solvent of TATA-BF4 to induce SAM formation on a heated (∼50 °C) Au substrate. We show by STM how to detect and distinguish TATA-BF4 from TATA platforms, which lost their BF4 counterions. Finally, we observe a change of the counterion position on the SAM during the STM scanning, which we explain by an electric-field-induced decrease of the electrostatic interaction in TATA-BF4 on the surface. We applied DFT calculations to reveal the influence of the gold lattice and the electric field of the STM tip on the stability of TATA-BF4 physisorbed on the surface.

Alkylthiol self-assembled monolayers on Au(111) with tailored tail groups for attaching gold nanoparticles.

Self-assembled monolayers (SAMs) on Au(111) are able to control the functionality of a gold surface. We use scanning tunnelling microscopy (STM) in air and contact angle measurements to compare the morphology and the chemistry of three alkylthiol SAMs differing by their tail groups: 1,9-nonanedithiol (NDT), 1,4-butanedithiol (BDT) and 11-mercaptoundecanol (MUOH). STM reveals very different morphologies: a hexagonal lattice for MUOH and parallel rows for NDT and BDT. In the case of NDT, we find that the thiol tail groups may form disulfide bridges with long immersion times. The availability of the -SH group for chemical reactions is demonstrated by attaching gold nanoparticles (AuNPs). When the thiol tail group is available, AuNPs readily attach as shown with atomic force microscopy (AFM). When disulfide bridges are formed, the gold surface is not able to bind nanoparticles.

Optical Properties of Gold Nanoparticle Assemblies on a Glass Surface.

The assemblies of cross-linked gold nanoparticles (AuNP) attract lot of scientific attention due to feasible perspectives of their use for development of scaled contact electrodes. Here, we developed and tested method of solid-state formation of dimers created from small AuNP (~18 nm) cross-linked with 1.9-nonadithiol (NDT) molecules. The morphology of created coating of a glass surface and its optical-polarization properties have been studied in detail by combination of scanning electron microscopy, atomic force microscopy, UV-visible spectroscopy, and modulation-polarization spectroscopy.The modification of localized surface plasmon resonance (LSPR) of single AuNP and their assemblies were studied by measuring of the spectral characteristics of polarization difference at all stages of synthesis. The radiative and nonradiative modes of LSPR have been analyzed in detail at different angles of incidence light. This allowed establishing relation between surface morphology of the coating and its optical properties.

Static and dynamic electronic characterization of organic monolayers grafted on a silicon surface.

Organic layers chemically grafted on silicon offer excellent interfaces that may open up the way for new organic-inorganic hybrid nanoelectronic devices. However, technological achievements rely on the precise electronic characterization of such organic layers. We have prepared ordered grafted organic monolayers (GOMs) on Si(111), sometimes termed self-assembled monolayers (SAMs), by a hydrosilylation reaction with either a 7-carbon or an 11-carbon alkyl chain, with further modification to obtain amine-terminated surfaces. X-ray photoelectron spectroscopy (XPS) is used to determine the band bending (∼ 0.3 eV), and ultraviolet photoelectron spectroscopy (UPS) to measure the work function (∼ 3.4 eV) and the HOMO edge. Scanning tunneling microscopy (STM) confirms that the GOM surface is clean and smooth. Finally, conductive AFM is used to measure electron transport through the monolayer and to identify transition between the tunneling and the field emission regimes. These organic monolayers offer a promising alternative to silicon dioxide thin films for fabricating metal-insulator-semiconductor (MIS) junctions. We show that gold nanoparticles can be covalently attached to mimic metallic nano-electrodes and that the electrical quality of the GOMs is completely preserved in the process.

Controlling the reproducibility of Coulomb blockade phenomena for gold nanoparticles on an organic monolayer/silicon system.

Two types of highly ordered organic layers were prepared on silicon modified with an amine termination for binding gold nanoparticles (AuNPs). These two grafted organic monolayers (GOMs), consisting of alkyl chains with seven or 11 carbon atoms, were grafted on oxide-free Si(111) surfaces as tunnel barriers between the silicon electrode and the AuNPs. Three kinds of colloidal AuNPs were prepared by reducing HAuCl4 with three different reactants: citrate (Turkevich synthesis, diameter ∼16 nm), ascorbic acid (diameter ∼9 nm), or NaBH4 (Natan synthesis, diameter ∼7 nm). Scanning tunnel spectroscopy (STS) was performed in a UHV STM at 40 K, and Coulomb blockade behaviour was observed. The reproducibility of the Coulomb behavior was analysed as a function of several chemical and physical parameters: size, crystallinity of the AuNPs, influence of surrounding surfactant molecules, and quality of the GOM/Si interface (degree of oxidation after the full processing). Samples were characterized with scanning tunneling microscope, STS, atomic force microscope, Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy (XPS), and high resolution transmission electronic microscope. We show that the reproducibility in observing Coulomb behavior can be as high as ∼80% with the Natan synthesis of AuNPs and GOMs with short alkyl chains.

A multiscale description of molecular adsorption on gold nanoparticles by nonlinear optical spectroscopy.

Nonlinear optical Sum and Difference-Frequency spectroscopies are used to probe and model the surface of thiophenol-functionalised gold nanoparticles grafted on a Si(100) substrate through two different silanization procedures. By scanning the [980-1100 cm(-1)] infrared spectral range with the CLIO Free Electron Laser, ring deformation vibrations of adsorbed thiophenol are investigated. Quantitative data analysis addresses three levels of organization: microscopic, nanoscopic and molecular. Grafting with p-aminophenyl-trimethoxysilane shows an increase of around 40% in surface density of nanoparticles (N(s)) as compared to 3-aminopropyl-triethoxysilane. The relative amplitudes of the resonant and nonresonant contributions to the SFG and DFG spectra are discussed in terms of N(s), Fresnel reflectivity factors and local amplification of the nonlinear signals by coupling to the surface plasmon of the particles. They are shown to quantitatively scale with N(s), as measured by atomic force microscopy. Vibration mode assignment is performed through a critical analysis of literature data on IR and Raman spectroscopies coupled to DFT calculations, for which a methodology specific to molecules adsorbed on gold atoms is discussed.

Raman spectroscopy of CaSnO3 at high temperature: a highly quasi-harmonic perovskite.

Calcium stannate perovskite (CaSnO(3)) has been studied by Raman spectroscopy at two excitation wavelengths (514.5 and 632.8 nm). No phase transition was observed. Rather, the thermal evolution of the Raman lines showed a high degree of harmonicity with small Grüneisen parameters and thermal line broadening following Γ=Acothθ/T, where the quantum temperature θ is determined by the phonon branch without further coupling with other degrees of freedom. The geometrical nature of phonon lines has been identified. High-temperature powder x-ray diffraction measurements provide thermal expansion coefficients of α(x)=13.9 × 10(-6) K(-1), α(y)=2.7 × 10(-6) K(-1), α(z)=14.3 × 10(-6) K(-1). The strongly quasi-harmonic behaviour observed and the lack of any indication of instability with respect to the post-perovskite structure points to the strongly first-order character of the reported perovskite to post-perovskite phase transition in this material, which appears to behave as a very good analogue to MgSiO(3) in the Earth's interior.

A phase transition close to room temperature in BiFeO3 thin films.

BiFeO3 (BFO) multiferroic oxide has a complex phase diagram that can be mapped by using appropriately substrate-induced strain in epitaxial films. By using Raman spectroscopy, we conclusively show that films of the so-called supertetragonal T-BFO phase, stabilized under compressive strain, display a reversible temperature-induced phase transition at about 100 °C, and thus close to room temperature.

Temperature-dependent Raman scattering of DyScO3 and GdScO3 single crystals.

We report a temperature-dependent Raman scattering investigation of DyScO(3) and GdScO(3) single crystals from room temperature up to 1200 °C. With increasing temperature, all modes decrease monotonically in wavenumber without anomaly, which attests to the absence of a structural phase transition. The high temperature spectral signature and extrapolation of band positions to higher temperatures suggest a decreasing orthorhombic distortion towards the ideal cubic structure. Our study indicates that this orthorhombic-to-cubic phase transition is close to or higher than the melting point of both rare-earth scandates ([Formula: see text]), which might exclude the possibility of the experimental observation of such a phase transition before melting. The temperature-dependent shift of Raman phonons is also discussed in the context of thermal expansion.

Raman study of CeO2 texture as a buffer layer in the CeO2/La2Zr2O7/Ni architecture for coated conductors.

The CeO(2)/La(2)Zr(2)O(7)/Ni piled-up structure is a very promising architecture for YBa(2)Cu(3)O(7) (YBCO) coated conductors. We have grown YBCO/CeO(2)/LZO/Ni epitaxial structures by metalorganic decomposition (MOD) and metalorganic chemical vapor deposition (MOCVD) methods. The crystallographic quality of the CeO(2) layer is not well determined by conventional X-ray diffraction (XRD) due to the superposition of LZO and CeO(2) reflections. An alternative simple Raman spectroscopy analysis of the crystalline quality of the CeO(2) films is proposed. The F(2g) Raman mode of CeO(2) can be quantified either by using two polarization configurations (crossed or parallel) or at two different rotation angles around the normal axis (0 degrees and 45 degrees ) to obtain information about the sample texture. The sample texture can be determined via a quality factor (referred to as the Raman intensity ratio, RIR) consisting of calculating the ratio of the integrated intensity of the CeO(2) F(2g) mode at 0 degrees and 45 degrees in parallel polarization. This factor correlates with superconducting performance and the technique can be used as an on-line nondestructive characterization method.

Raman scattering of perovskite DyScO(3) and GdScO(3) single crystals.

We report an investigation of DyScO(3) and GdScO(3) single crystals by Raman scattering in various scattering configurations and at various wavelengths. The Raman spectra are well defined and the reported spectral signature together with the mode assignment set the basis for the use of Raman scattering for the investigation of rare earth scandates. The observed positions of Raman modes for DyScO(3) are for most bands in reasonable agreement with recent theoretical ab initio predictions of the vibrational spectrum for the same material. Further to the phonon signature, a luminescence signal is observed for both scandates. While the luminescence is weak for DyScO(3), it is very intense for GdScO(3) when using a 488 or 514 nm excitation line, which in turn inhibits full analysis of the phonon spectrum. We show that a meaningful phonon Raman analysis of GdScO(3) samples can be done by using a 633 nm excitation.

Probing the Si-Si dimer breaking of Si(100)2x1 surfaces upon molecule adsorption by optical spectroscopy.

The adsorption of atoms and molecules of several gases of the Si(100)2x1 silicon reconstructed surface is investigated by surface differential reflectance spectroscopy. This UV-visible optical spectroscopy makes possible the discrimination between two adsorption modes, depending on whether or not the adsorption leads to breaking the Si-Si dimers. The observation of two different optical features is assigned to the bonding on dangling bonds or to the breaking of dimers, and gives access to the adsorption mode of hydrogen, water, oxygen, and pyridine. Moreover, the technique being quantitative, we can determine the total amount of dimers involved in the adsorption and monitor the adsorption kinetics.