MoVN-Cu Coatings for In Situ Tribocatalytic Formation of Carbon-Rich Tribofilms in Low-Viscosity Fuels.

Inhibiting the tribological failure of mechanical assemblies which rely on fuels for lubrication is an obstacle to maintaining the lifetime of these systems with low-viscosity and low-lubricity fuels. In the present study, a MoVN-Cu nanocomposite coating was tribologically evaluated for durability in high- and low-viscosity fuels as a function of temperature, load, and sliding velocity conditions. The results indicate that the MoVN-Cu coating is effective in decreasing wear and friction relative to an uncoated steel surface. Raman spectroscopy, transmission electron microscopy, and electron-dispersive spectroscopy analysis of the MoVN-Cu worn surfaces confirmed the presence of an amorphous carbon-rich tribofilm which provides easy shearing and low friction during sliding. Further, the characterization of the formed tribofilm revealed the presence of nanoscale copper clusters overlapping with the carbon peak intensities supporting the tribocatalytic origin of the surface protection. The tribological assessment of the MoVN-Cu coating reveals that the coefficient of friction decreased with increasing material wear and initial contact pressure. These findings suggest that MoVN-Cu is a promising protective coating for fuel-lubricated assemblies due to its adaptive ability to replenish lubricious tribofilms from hydrocarbon environments.

Revealing the Buried Metal-Organic Interface: Restructuring of the First Layer by van der Waals Forces.

With the use of molecular manipulation in a cryogenic scanning tunneling microscope, the structure and rearrangement of sexiphenyl molecules at the buried interface of the organic film with the Cu(110) substrate surface have been revealed. It is shown that a reconstruction of the first monolayer of flat lying molecules occurs due to the van der Waals pressure from subsequent layers. In this rearrangement, additional sexiphenyl molecules are forced into the established complete monolayer and adopt an edge-on configuration. Incorporation of second layer molecules into the first layer is also demonstrated by purposely pushing sexiphenyl molecules with the STM tip. The results indicate that even chemisorbed organic layers at interfaces can be significantly influenced by external stress from van der Waals forces of subsequent layers.

Alternating chirality in the monolayer H2TPP on Cu(110)-(2 × 1)O.

In this work, the structure of the tetraphenylporphyrin (H2TPP) monolayer grown on the oxygen passivated Cu(110)-(2 × 1)O surface has been investigated with LT-STM and elucidated by DFT-calculations. The monolayer is commensurate with all molecules occupying the same adsorption site, but there are two molecules per unit cell. The STM images suggest alternating chirality for the molecules within one unit cell which is supported by DFT total energy calculations for monolayers on the Cu-O substrate. STM simulations for alternating and single chirality monolayers have subtle differences which indicate that the experimentally observed surface is one containing molecules with alternating chirality, that is racemicity within the unit cell.

Layer resolved evolution of the optical properties of α-sexithiophene thin films.

We report a combined reflectance difference spectroscopy and scanning tunneling microscopy study of ultrathin α-sexithiophene (6T) films deposited on the Cu(110)-(2×1)O surface. The correlation between the layer resolved crystalline structure and the corresponding optical spectra data reveals a highly sensitive dependence of the excitonic optical properties on the layer thickness and crystalline structure of the 6T film.

Crystal growth of para-sexiphenyl on clean and oxygen reconstructed Cu(110) surfaces.

The formation of crystalline para-sexiphenyl (6P) films on Cu(110) and Cu(110)-(2 × 1)O (Cu-O) has been studied by low energy electron diffraction, X-ray absorption spectroscopy and both in situ and ex situ X-ray diffraction methods to elucidate the transition from the initial monolayers to crystalline thin films. It is found that, for Cu-O, a single and, for Cu(110), a double wetting layer is formed which then acts as a template for the subsequent 3D crystal growth. For both substrates the orientation of the long molecular axes of the 6P molecules in the first layers is conserved for the molecules in the bulk crystals growing on them. The main difference between both systems is that on Cu-O the first monolayer assembles in a form close to that of a 6P bulk plane which can be easily continued by crystallites grown upon them, while on the Cu(110) surface the 6P mono- and bi-layers differ substantially from the bulk structure. The bi-layer forms a complex periodically striped phase. Thin 6P films grow with the 6P(203) crystal plane parallel to the Cu-O substrate surface. For this orientation, the 6P molecules are stacked in layers and the molecules demonstrate only one tilt of the mean molecular plane with respect to the sample surface. On clean Cu(110), a more complex 6P(629) plane is parallel to the substrate surface and this orientation is likely a consequence of the super-molecular long-range periodicity of the second molecular layer striped phase.

A momentum space view of the surface chemical bond.

Well-ordered and oriented monolayers of conjugated organic molecules can offer new perspectives on surface bonding. We will demonstrate the importance of the momentum distribution, or symmetry, of the adsorbate molecules' π orbitals in relation to the states available for hybridization at the metal surface. Here, the electronic band structure of the first monolayer of sexiphenyl on Cu(110) has been examined in detail with angle-resolved ultraviolet photoemission spectroscopy over a large momentum range and will be compared to measurements of a multilayer thin film and to density functional calculations. In the monolayer, the one-dimensional intramolecular band structure can still be recognized, allowing an accurate determination of orbital modification upon bonding and the relative energetic positions of the electronic levels. It is seen that the character of the molecular π orbitals is largely maintained despite strong mixing between Cu and molecular states and that the lowest unoccupied molecular orbital (LUMO) is filled by hybridization with Cu s,p states rather than through a charge transfer process. It is also shown that the momentum distribution of the substrate states involved and the periodicity of the molecular overlayer play a large role in the final E(k) distribution of the hybrid states. The distinct momentum distribution of the LUMO, interacting with the Cu substrate s,p valence bands around the gap in the surface projection of the bulk band structure, make this system a particularly illustrative example of momentum resolved hybridization. This system demonstrates that, for hybridization to occur, not only do states require overlap in energy and space, but also in momentum.

Pre-nucleation dynamics of organic molecule self-assembly investigated by PEEM.

Pre-nucleation dynamics, nucleation and templated self-assembly of a conjugated planar aromatic molecule are investigated by photoemission electron microscopy (PEEM). The high resolution of individual molecular layers in PEEM, in combination with a numerical simulation, reveals the dynamic behaviour of molecules during the pre-nucleation deposition period and their temperature dependence. The in situ deposition of p-sexiphenyl (6P) molecules on Cu(110) and Cu(110) 2 × 1-O surfaces in ultrahigh vacuum, when monitored by PEEM in real-time allows (a) layer densities, (b) meta-stable layer filling by 6P molecules, (c) dynamic surface redistributions during layer filling and (d) critical density spontaneous dewetting to be accurately measured. The comparison of 6P deposited on Cu(110) to Cu(110) 2 × 1-O enables temperature dependent 6P nucleation processes on Cu(110) to be elucidated from PEEM. The interplay between energetically stable molecular arrangements and kinetically stabilised arrangements is shown to dominate the pre- and post-nucleation processes. In combination with additional data obtained during post-nucleation deposition times, such as surface diffusion anisotropies and nucleation energies, it is concluded that the pre-requisite for 6P nucleation, in a lying down orientation, is the formation of a double tilted layer with at least one layer being meta-stable.

Revealing the buried interface: para-sexiphenyl thin films grown on TiO2(110).

The thickness dependent optical and electronic structure of para-sexiphenyl thin films grown on TiO(2)(110) at around 400 K reveals that the substrate is first wet by one monolayer of molecules lying with their long axis parallel to the [001] direction of the substrate, while the molecules in subsequent layers are almost standing upright. Whilst ultraviolet photoemission spectroscopy (UPS) is sensitive to the molecules in the outermost layer, reflection difference spectroscopy (RDS) shows that the molecules at the buried interface do not dewet and maintain the orientation of the original wetting monolayer.

Reconstruction of molecular orbital densities from photoemission data.

Photoemission spectroscopy is commonly applied to study the band structure of solids by measuring the kinetic energy versus angular distribution of the photoemitted electrons. Here, we apply this experimental technique to characterize discrete orbitals of large pi-conjugated molecules. By measuring the photoemission intensity from a constant initial-state energy over a hemispherical region, we generate reciprocal space maps of the emitting orbital density. We demonstrate that the real-space electron distribution of molecular orbitals in both a crystalline pentacene film and a chemisorbed p-sexiphenyl monolayer can be obtained from a simple Fourier transform of the measurement data. The results are in good agreement with density functional calculations.

The molecular orientation of para-sexiphenyl on Cu(110) and Cu(110) p(2x1)O.

Controlling the molecular growth of organic semiconductors is an important issue to optimize the performance of organic devices. Conjugated molecules, used as building blocks, have an anisotropic shape and also anisotropic physical properties like charge transport or luminescence. The main challenge is to grow highly crystalline layers with molecules of defined orientation. The higher the crystallinity, the closer these properties reach their full intrinsic potential, while the orientation determines the physical properties of the film. Herein we show that the molecular orientation and growth can be steered by the surface chemistry, which tunes the molecule-substrate interaction. In addition, the oxygen reconstruction of the surface, demonstrates the flexibility of the organic molecules to adopt a given surface corrugation and their unique possibility to release stress by tilting.

Heteroepitaxy of organic-organic nanostructures.

Highly crystalline organic heteroepitaxial layers with controlled molecular orientations and morphologies are one of the keys for optimum organic device performance. With studies of molecular orientation, structure, and morphology, we have investigated the ability of oriented organic films to act as substrate templates for the growth of a second organic layer. Depending on the molecular orientation in the sexiphenyl substrate, crystalline sexithiophene nanostructures of either pyramidal or needlelike morphology, with either near vertical or parallel molecular orientations, respectively, grow.