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Understanding the physical–chemical processes ruling the interaction of particles (atoms, molecules, and ions) with surfaces is fundamental in several research fields, such as heterogeneous catalysis, astrochemistry, and nuclear fusion. In particular, the interaction of hydrogen isotopes with plasma facing materials represents a high-priority research task in the fusion community. Such studies are essential to ensure the successful operation of experimental fusion reactors, such as the tokamak ITER. In this work, we present a surface science apparatus developed to study ion-surface interaction in fusion relevant systems. It combines laser-based techniques with contaminant-free ion/molecular beams, mass spectrometry, and surface science tools such as low-energy electron diffraction and Auger electron spectroscopy. It allows to cover a wide range of sample temperatures, from 130 to 2300 K, by changing the heating rate of samples from 0.1 to 135 K/s and maintaining the linearity of the heating ramps, a powerful feature to gain insight on adsorption, absorption, and desorption mechanisms. Experimental calibration and performance are presented in detail. Moreover, to provide a factual overview of the experimental capabilities, we focus on two different applications: the protocol used to clean a W(110) single crystal sample and the development of laser temperature programmed desorption to study helium retention in tungsten. [ABSTRACT FROM AUTHOR]

This article, titled "Laser temperature programmed desorption: A flexible technique to study ion-surface interaction," was published in the Review of Scientific Instruments. It was originally published online on March 7, 2024, but was missing information from the Acknowledgments section. The missing information has since been reinstated, acknowledging that the work was carried out within the framework of the French Federation for Magnetic Fusion Studies (FR-FCM) and received funding from Aix-Marseille University and the ANR. AIP Publishing has apologized for the error and corrected all online versions of the article on March 8, 2024. The authors of the article are M. Minissale, A. Dunand, P. Hiret, J.-B. Faure, C. Grisolia, T. Angot, L. Gallais, and R. Bisson. [Extracted from the article]

This article deals with surface loss on quartz of atomic hydrogen (H) and its isotope deuterium (D) in a low-pressure (10 Pa) pulsed inductively coupled plasma. The atomic temporal decay in the post discharge is measured by two-photon absorption laser-induced fluorescence (TALIF). From the loss rate, the atomic surface loss probability is determined. In pure hydrogen or pure deuterium gas, no isotopic effect on surface kinetics has been observed and the surface loss probabilities of H and D were found to be almost identical and equal to ∼1.8%. However, despite the lack of difference in surface loss probability, a net isotopic effect on surface loss rate due to the mass difference between the isotopes is measured. Hydrogen atoms diffuse faster and have higher flux to the plasma chamber walls than deuterium atoms. Hydrogen atoms are therefore lost at higher rate than deuterium atoms. Based on the observed isotopic difference and on the comparison between H and D TALIF signals, the isotopic effects on H and D atom production are discussed. [ABSTRACT FROM AUTHOR]

The interaction of H atoms having relatively low average kinetic energy (∼0.025 eV) with both perfectly clean and D-covered HOPG surfaces is investigated using high resolution electron energy loss spectroscopy. From this study we confirm, in a controlled fashion, the presence of the theoretically predicted adsorption barrier since no adsorption is detected for such H atoms on HOPG. Moreover, we demonstrate that the exposure of a D saturated HOPG surface to these H atoms results in the complete removal of adatoms, with no further adsorption despite the prediction of the adsorption barrier to vanish for H dimers in para configuration. Therefore, the recombinative abstraction mechanism which competes with the adsorption process is more efficient. [ABSTRACT FROM AUTHOR]

Organic-metal interfaces, in particular, self-assembling systems, are interesting in the field of molecular electronics. In this study, we have investigated the formation of the Ag(110)-iron phthalocyanine (FePc) interface in a coverage range of less than 1 and up to 2 ML using synchrotron based photoelectron spectroscopy and low energy electron diffraction. As-deposited FePc forms a densely packed first layer exhibiting a 3×2/c(6×2) symmetry. Upon thermal treatment the order at the interface is modified depending on the initial FePc coverage, resulting in less densely packed but still ordered superstructures. The first monolayer is relatively strongly bound to the substrate, leading to the formation of an interface state just below the Fermi level. The highest occupied molecular orbital of FePc in the second layer is found at 1 eV higher binding energy compared to the interface state. [ABSTRACT FROM AUTHOR]

The adsorption of H/D atoms on the graphite (0001) surface is investigated by means of both high-resolution electron-energy loss spectroscopy (HREELS) and periodic first-principle density-functional theory. The two methods converge towards two modes of adsorption: adsorption in clusters of about four hydrogen atoms and adsorption in pairs of atoms on contiguous carbon sites. The desorption energies estimated from the calculated dissociation energies range from 8 to 185 kJ mol-1 leading to an estimated surface coverage at saturations of 30–44 at. %. These results are compared with previous thermal desorption spectroscopy results. New HREEL signal assignments are proposed based on quantum calculations. [ABSTRACT FROM AUTHOR]

We present a comparative high-resolution electron energy-loss spectroscopy study on the interaction of atomic hydrogen and deuterium with various reconstructions of SiC(0 0 0 1). We first show that on both the (3 × 3) and reconstructions, deuterium atoms only bind to silicon atoms, thereby confirming the silicon-rich appellation of these reconstructions. Deuterium passivation of the (3 × 3) is only reversible when exposed to atomic deuterium at a surface temperature of 700 K since tri- and dideuterides, necessary precursors for silicon etching, are not stable. On the other hand, we show that the deuteration of the is always reversible because precursors to silicon etching are scarce on the surface. Then, we demonstrate that hydrogen (deuterium) adsorption at 300 K on both the (buffer-layer) and the quasi-free-standing graphene occurs on carbon atoms justifying their carbon-rich appellation. Comparison of the deuterium binding in the intercalation layer of quasi-free-standing graphene with the deuterated surface provides some indication on the bonding structure at the substrate intercalation layer. Finally, by measuring C–H (C–D) vibrational frequencies and hydrogen (deuterium) desorption temperatures we suggest that partial sp2-to-sp3 rehybridization occurs for the carbon atoms of the buffer-layer because of the corrugation related to covalent bonding to the SiC substrate. In contrast, on quasi-free-standing graphene hydrogen (deuterium) atoms adsorb similarly to what is observed on graphite, i.e. without preferential sticking related to the underlying SiC substrate. [ABSTRACT FROM AUTHOR]

An ultrahigh vacuum chamber has been developed for structural analysis of adsorbed films and single-crystal surfaces using synchrotron x-ray diffraction. It is particularly well suited for investigations of physisorbed and other weakly bound films. The chamber is small enough to transport and mount directly on a standard four-axis diffractometer and can also be used independently of the x-ray diffractometer. A low-current, pulse-counting, low-energy electron diffraction/Auger spectroscopy system with a position-sensitive detector enables in situ characterization of the film and substrate while the sample is located at the x-ray scattering position. A closed-cycle He refrigerator and electron bombardment heater provide controlled substrate temperatures from 30 to 1300 K. The chamber is also equipped with an ion sputter gun, a quadrupole mass spectrometer, and a gas handling system. Details of the design and operation of the instrument are described. To demonstrate the performance of the instrument, we present some preliminary results of a study of Xe physisorbed on the Ag(111) surface. [ABSTRACT FROM AUTHOR]

Presents a study on the catalytical decomposition of a disilane and germane mixture on silicon. Limitation of the thermal stability of the various germanium hydrides phases; Utilization of decomposed gas mixture in the study; Optimal conditions for the preparation of Si[sub 1-x]Ge[sub x].

A simple, original and easy to construct, in situ crystal cleaver is presented. It is mounted directly on the sample holder and is particularly suitable for low temperature experiments. It is small enough to be adaptable on any low temperature x, y, z, Θ, φ manipulator. Cleaving in situ allows one to obtain a uniform and well-constructed single crystal surface. Adsorption experiments of krypton monolayers on an MgO (100) in situ cleaved crystal at 44 K are presented. [ABSTRACT FROM AUTHOR]

We report on the observation of a low-energy surface plasmon mode in the case of a highly ordered organic monolayer adsorbed onto a metallic substrate. Careful investigation using high-resolution electron energy loss spectroscopy, tuning the kinematics, demonstrates that this mode presents a strong energy dependence with the transferred momentum. We treated this mode using a Drude ansatz and discussed its positive quadratic dispersion. We established the physical origin of this surface plasmon as due to a space-charge region arising from an electron-vibration coupling at the interface between the organic monolayer and the metallic substrate. The existence of a space-charge region at an organic-metal interface is of particular interest as it brings a new enlightenment in the understanding of the physical mechanisms involved at such interfaces, of which charge injection plays a decisive role for device performances. [ABSTRACT FROM AUTHOR]

The electronic structure of cobalt-phthalocyanine (CoPc) molecules adsorbed on Ag(100) is investigated by photoemission spectroscopy. The results are compared to first-principles electronic structure calculations, based on many-body perturbation theory in the GW approximation. The photoemission data, obtained from both multilayer and monolayer films of CoPc, show that charge transfer occurs between the first molecular layer and the metal surface. Varying the photon energy, to tune the photoionization cross sections, reveals that the charge-transfer-related interface states mainly involve the Co 3d atomic orbitals of the Co central atom. GW calculations for the neutral CoPc molecule and its anion compare well with the experimental observations for a multilayer and a monolayer CoPc film, respectively. They confirm the major role played by the Co atom in the charge-transfer process and elucidate the complex energy rearrangement of the molecular electronic levels upon metal adsorption. [ABSTRACT FROM AUTHOR]

Adsorption of organic molecules on well-oriented single-crystal coinage metal surfaces fundamentally affects the energy distribution curve of ultraviolet photoelectron spectroscopy spectra. New features not present in the spectrum of the pristine metal can be assigned as "interface states" having some degree of molecule-substrate hybridization. Here it is shown that interface states having molecular orbital character can easily be identified at low binding energy as isolated features above the featureless substrate sp plateau. On the other hand, much care must be taken in assigning adsorbate-induced features when these lie within the d-band spectral region of the substrate. In fact, features often interpreted as characteristic of the molecule-substrate interaction may actually arise from substrate photoclectrons scattered by the adsorbates. This phenomenon is illustrated through a series of examples of noble-metal single-crystal surfaces covered by monolayers of large π-conjugated organic molecules. [ABSTRACT FROM AUTHOR]

Hydrogenation of deuterium-intercalated quasi-free-standing monolayer graphene on SiC(0001) is obtained and studied with low-energy electron diffraction and high-resolution electron energy loss spectroscopy. While the carbon honeycomb structure remains intact, it is shown that a significant band gap opens in the hydrogenated material. Vibrational spectroscopy evidences for hydrogen chemisorption on the quasi-free-standing graphene is provided and its thermal stability is studied. [ABSTRACT FROM AUTHOR]

Chemical functionalization of graphene is one method pursued to engineer new properties into a graphene sheet. Graphene oxide is the most commonly used chemical derivative of graphene. Here we present experimental evidence for the formation of enolate moieties when oxygen atoms are added to the graphene basal plane. The exotic functional groups are stabilized by simultaneous bond formation between the graphene sheet and the underlying Ir(111) substrate. Scanning tunneling microscopy images demonstrate the patterned nature of C-O bond formation and X-ray photoelectron spectroscopy and high-resolution electron energy loss spectroscopy are used to characterize the enolate moiety. The results present a new mechanism for the formation of patterned graphene oxide and provide evidence of a functional group rarely considered for graphene oxide materials.

Original reaction pathways can be explored in the on-surface synthesis approach where small aromatic precursors are confined to the surface of single crystal metals. The bis-indanedione molecule reacted with itself on silver surfaces in different ways, through a Knoevenagel reaction or an oxidative coupling, leading to the formation of a variety of new molecular compounds and covalently-linked 1D or 2D networks. Noteworthy, original reaction products were obtained that cannot be synthesized in traditional solvent-based chemistry. The lowest activation temperature for the homo-coupling reactions was found on the Ag(111) surface. The Ag(110) was highly selective in terms of coupling reaction type, while on Ag(100) the temperature could finely control the selectivity. The on-surface synthesis approach is shown here to be particularly efficient to produce original compounds in mild conditions, using activation temperatures as low as 200 °C. The different structures were characterized by scanning tunnelling microscopy (STM) together with X-ray photoelectron emission spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS)., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hydrogen functionalization of graphene by exposure to vibrationally excited H 2 molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H 2 molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H 2 dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H-H bond. The first reacting H 2 molecule must contain considerable vibrational energy to overcome the dissociative adsorption barrier. However, this initial adsorption further activates the surface resulting in reduced barriers for dissociative adsorption of subsequent H 2 molecules. This enables functionalization by H 2 molecules with lower vibrational energy, yielding an avalanche effect for the hydrogenation reaction. These results provide an example of a catalytically active graphene-coated surface and additionally set the stage for a re-interpretation of previous experimental work involving elevated H 2 background gas pressures in the presence of hot filaments.

In the blooming field of on-surface synthesis, molecular building blocks are designed to self-assemble and covalently couple directly on a well-defined surface, thus allowing the exploration of unusual reaction pathways and the production of specific compounds in mild conditions. Here we report on the creation of functionalized organic nanoribbons on the Ag(110) surface. C-H bond activation and homo-coupling of the precursors is achieved upon thermal activation. The anisotropic substrate acts as an efficient template fostering the alignment of the nanoribbons, up to the full monolayer regime. The length of the nanoribbons can be sequentially increased by controlling the annealing temperature, from dimers to a maximum length of about 10 nm, limited by epitaxial stress. The different structures are characterized by room-temperature scanning tunnelling microscopy. Distinct signatures of the covalent coupling are measured with high-resolution electron energy loss spectroscopy, as supported by density functional theory calculations.