Helium Atom Scattering Research Articles

Correlating Electron–Phonon Coupling and In Situ High-Temperature Atomic-Scale Surface Structure at the Metallic Nb(100) Surface by Helium Atom Scattering and Density Functional Theory

Correlating Electron–Phonon Coupling and In Situ High-Temperature Atomic-Scale Surface Structure at the Metallic Nb(100) Surface by Helium Atom Scattering and Density Functional Theory

The Electron–Phonon Interaction at Vicinal Metal Surfaces Measured with Helium Atom Scattering

Recently, it was demonstrated that inelastic helium atom scattering from conducting surfaces provides a direct measurement of the surface electron–phonon coupling constant (mass enhancement factor λ) via the temperature or the incident wave vector dependence of the Debye–Waller exponent. Here, previous published as well as unpublished helium atom scattering diffraction data from the vicinal surfaces of copper (Cu(11α), with α = 3, 5, 7) and aluminum (Al(221) and Al(332)) were analyzed to determine λ. The results suggested an enhancement with respect to the corresponding data for the low-index surfaces (111) and (001) above the roughening transition temperature. The specific role of steps compared to that of terraces is briefly discussed.

Measuring the Electron–Phonon Interaction in Two-Dimensional Superconductors with He-Atom Scattering

Helium-atom scattering (HAS) spectroscopy from conducting surfaces has been shown to provide direct information on the electron–phonon interaction, more specifically the mass-enhancement factor λ from the temperature dependence of the Debye–Waller exponent, and the mode-selected electron–phonon coupling constants λQν from the inelastic HAS intensities from individual surface phonons. The recent applications of the method to superconducting ultra-thin films, quasi-1D high-index surfaces, and layered transition-metal and topological pnictogen chalcogenides are briefly reviewed.

Terahertz surface modes and electron-phonon coupling on Bi2Se3 (111)

We present a combined experimental and theoretical study of the surface vibrational modes of the topological insulator (TI) Bi$_2$Se$_3$ with particular emphasis on the low-energy region below 10 meV that has been difficult to resolve experimentally. By applying inelastic helium atom scattering (HAS), the entire phonon dispersion was determined and compared with density functional perturbation theory (DFPT) calculations. The intensity of the phonon modes is dominated by a strong Rayleigh mode, in contrast to previous experimental works. Moreover, also at variance with recent reports, no Kohn-anomaly is observed. These observations are in excellent agreement with DFPT calculations. Besides these results, the experimental data reveal$-$via bound-state resonance enhancement$-$two additional dispersion curves in the gap below the Rayleigh mode. They are possibly associated with an excitation of a surface electron density superstructure that we observe in HAS diffraction patterns. The electron-phonon coupling paramenter $\lambda$ = 0.23 derived from our temperature dependent Debye-Waller measurements compares well with values determined by angular resolved photoemission or Landau level spectroscopy. Our work opens up a new perspective for THz measurements on 2D materials as well as the investigation of subtle details (band bending, the presence of quantum well states) with respect to the electron-phonon coupling.

Origin of the Electron-Phonon Interaction of Topological Semimetal Surfaces Measured with Helium Atom Scattering.

He atom scattering has been demonstrated to be a sensitive probe of the electron–phonon interaction parameter λ at metal and metal-overlayer surfaces. Here it is shown that the theory linking λ to the thermal attenuation of atom scattering spectra (the Debye–Waller factor) can be applied to topological semimetal surfaces, such as the quasi-one-dimensional charge-density-wave system Bi(114) and the layered pnictogen chalcogenides. The electron−phonon coupling, as determined for several topological insulators belonging to the class of bismuth chalcogenides, suggests a dominant contribution of the surface quantum well states over the Dirac electrons in terms of λ.

Experimental determination of surface thermal expansion and electron–phonon coupling constant of 1T-PtTe2

We report an extensive structural characterization of the surface of 1T-PtTe2 crystals by means of helium atom scattering (HAS) and ultra-high resolution scanning tunnelling microscopy (STM). HAS reveals that this bi-dimensional surface presents a large structural corrugation (∼) in direction. The surface lattice constant of PtTe2 derived from the positions of the helium diffraction peaks up to fifth order was found to be , in agreement with STM and x-ray diffraction measurements. This value remains unchanged in the temperature range between 90 and 580 K. These findings suggest that 1T-PtTe2 behaves similarly to graphene on a weakly-interacting substrate, for which the surface thermal expansion coefficient is zero within experimental error. The electron–phonon coupling constant has been determined by recording the thermal attenuation of the elastic diffraction peaks of PtTe2. Based on a recently developed quantum theoretical method adapted to layered degenerate semiconductors we find that lies between 0.38–0.42.

Statics and dynamics of multivalley charge density waves in Sb(111)

Charge density waves (CDWs), periodic modulations of the charge density, are among the most abundant and non-trivial ordered phases in condensed matter. Here we demonstrate the occurrence of multi-valley charge density waves (MV-CDW) on the semimetal Sb(111), a phenomenon previously observed at semiconductor surface inversion layers. The topological nature of the pocket surface states in Sb(111) ensures perfect nesting conditions giving rise to sharp peaks in helium atom scattering (HAS) diffraction spectra. The peculiar temperature dependence permits to distinctly associate the diffraction peaks with surface electron and hole-pocket states due to the non-trivial surface electronic band structure known from recent experimental data and present ab-initio calculations. Inelastic HAS spectra, besides providing the surface phonon dispersion curves in agreement with density functional perturbation theory calculations, reveal two additional dispersion curves of elementary excitations in the gap well below Rayleigh waves. They are attributed to collective excitations of the quasi-commensurate MV-CDWs associated with the surface electron M-pocket states at the Fermi level. These findings suggest that HAS can be regarded as a choice spectroscopy for the investigation of surface electronic excitations in the THz domain, opening up a new window for the search of collective phases at surfaces.

Electron–Phonon Coupling Constant of 2H-MoS2(0001) from Helium-Atom Scattering

We have studied the (0001) surface of 2H-MoS2 by means of helium-atom scattering (HAS). The electron–phonon coupling constant, λ, of this system has been determined by measuring the thermal attenua...

Prominent out-of-plane diffraction in helium scattering from a methyl-terminated Si(111) surface.

Due to their electrochemical and oxidative stability, organic-terminated semiconductor surfaces are well suited to applications in, for example, photoelectrodes and electrochemical cells, which explains the lively interest in their detailed characterization. Helium atom scattering (HAS) is a useful tool to carry out such characterization. Here, we have simulated HAS in He/CH3-Si(111) based on density functional theory (DFT) potential energy surfaces (PESs) and multi-configuration time-dependent Hartree (MCTDH) dynamics. Our analysis of HAS shows that most diffraction taking place in this system corresponds to high-order out-of-plane peaks. This is a general trend that does not depend on the specific features of the simulations, such as the inclusion or not of the van der Waals long-range effects. This is the first and only He-surface system for which such huge out-of-plane diffraction has been described. This striking theoretical finding should encourage new experimental developments to confirm this previously unreported effect.

A simple means of producing highly transparent graphene on sapphire using chemical vapor deposition on a copper catalyst

Chemical vapor deposition (CVD) is one of the best ways to scalably grow low cost, high quality graphene on metal substrates; unfortunately, it not ideal for producing graphene on dielectric substrates. Here, we demontrate production of a high quality graphene layer on Sapphire using CVD with a copper catalyst. The catalyst consists of a thin copper film grown epitaxially on α-Al2O3 (0001). After CVD growth of Graphene, the copper can be removed by simple evaporation in the presence of a carbon source (C2H4). We characterized the resulting graphene layer using Raman spectroscopy, atomic force microscopy (AFM), optical transmission and helium atom scattering (HAS). The sample exhibited a reduced Raman D peak and an excellent 2D to G ratio. AFM and HAS show large graphene domains over a macroscopic region. We measured >86% transparency over the visible spectrum.

Resolving localized phonon modes on graphene/Ir(111) by inelastic atom scattering

Low energy (few meV) acoustic phonon modes of graphene/Ir (111) have been measured using inelastic helium atom scattering (HAS). The data clearly show two vibrational modes with energies 4.6 and 7.2 meV at Γ¯ with dispersionless branches due to Umklapp scattering. The phonons observed are not the ones expected for a free-standing graphene monolayer, in spite of the weak interaction between graphene and Ir (111). The measured parabolic dispersion of the flexural mode along the ΓM¯ direction allows determining the bending rigidity κ=(0.80±0.07)eV. Inelastic HAS measured at diffraction conditions proves that the moiré superstructure results in localized phonon modes related to the upper and the lower regions of the graphene superstructure. Our study shows that inelastic HAS is suitable to resolve low-energy vibrations spatially localized on structures in the nanometer range.

Surface lattice dynamics and electron-phonon interaction in cesium ultra-thin films.

The phonon dispersion curves of ultrathin films of Cs(110) on Pt(111) measured with inelastic helium atom scattering (HAS) are reported and compared with density-functional perturbation theory (DFPT) calculations. The combined HAS and DFPT analysis also sheds light on the bulk phonon dynamics of bcc-Cs, on which very little is known from neutron scattering due to its large neutron capture cross-section. Moreover the temperature dependence of the elastic HAS Debye-Waller exponent of Cs(110)/Cu(111) ultrathin films allows for an estimation of the electron-phonon coupling strength λ as a function of the film thickness.

Surface Dynamics of the Wetting Layers and Ultrathin Films on a Dynamic Substrate: (0.5–4) ML Pb/Cu(111)

The growth of Pb ultrathin films on Cu(111) has been long studied in connection with electronic quantum-size effects and for the different temperature-dependent growth kinetics. At low temperature the formation of a wetting layer (1 monolayer (ML)), is followed by an instability of the 2 ML film and a regular layer-by-layer growth is then only observed for more than two monolayers. The 2 ML film was, however, shown to be stabilized by alloying Pb with 20% Tl. This work presents a theoretical study of the dynamics of the wetting layer as well as for 2 ML Pb0.8Tl0.2, 3 and 4 ML Pb on Cu(111) in the 4 × 4 commensurate phase, for which detailed inelastic Helium atom scattering (HAS) spectra have been measured. The present calculations based on the embedded atom method (EAM) include the dynamics of the substrate. Besides leading to a detailed interpretation of the HAS experimental data, the present results are compared with a previous density-functional perturbation theory (DFPT) study for 3 to 7 ML Pb on a ri...

Vibrational properties at the ordered metallic surface alloy system Au(110)-1×2-Pd

We present a calculation for the vibrational properties of the ordered surface alloy Au(110)-1×2-Pd on a crystalline substrate of Au. The surface phonon dispersion curves and the local vibrations densities of states (LDOS) are calculated in the harmonic approximation for the system, using the phase field matching theory (PFMT) method and associated real space Green’s functions. In particular, it is shown that the surface alloy presents optic vibrational modes above the Au bulk bands, along the directions of high-symmetry [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] of the corresponding two-dimensional Brillouin zone. Measurements of the surface phonon dispersion branches can hence be made by different techniques such as helium atom scattering (HAS) to compare with. The calculated LDOS for Au and Pd atomic sites in the four top surface atomic layers span a wider range of frequencies than those for the individual Au(110) or Pd(110) metallic surfaces. These LDOS provide a spectral signature for the progressive transition from the surface dynamics to that of the Au crystal bulk. Knowledge of these LDOS for the surface alloy can also serve as an input for modeling the diffusion and reaction rates of chemical species at its surface.

Continuous Compressed Sensing for Surface Dynamical Processes with Helium Atom Scattering.

Compressed Sensing (CS) techniques are used to measure and reconstruct surface dynamical processes with a helium spin-echo spectrometer for the first time. Helium atom scattering is a well established method for examining the surface structure and dynamics of materials at atomic sized resolution and the spin-echo technique opens up the possibility of compressing the data acquisition process. CS methods demonstrating the compressibility of spin-echo spectra are presented for several measurements. Recent developments on structured multilevel sampling that are empirically and theoretically shown to substantially improve upon the state of the art CS techniques are implemented. In addition, wavelet based CS approximations, founded on a new continuous CS approach, are used to construct continuous spectra. In order to measure both surface diffusion and surface phonons, which appear usually on different energy scales, standard CS techniques are not sufficient. However, the new continuous CS wavelet approach allows simultaneous analysis of surface phonons and molecular diffusion while reducing acquisition times substantially. The developed methodology is not exclusive to Helium atom scattering and can also be applied to other scattering frameworks such as neutron spin-echo and Raman spectroscopy.

Correction to "Electron-Phonon Coupling Strength at Metal Surfaces Directly Determined from the Helium Atom Scattering Debye-Waller Factor".

Correction to "Electron-Phonon Coupling Strength at Metal Surfaces Directly Determined from the Helium Atom Scattering Debye-Waller Factor".

Electron-Phonon Coupling Strength at Metal Surfaces Directly Determined from the Helium Atom Scattering Debye-Waller Factor.

A new quantum-theoretical derivation of the elastic and inelastic scattering probability of He atoms from a metal surface, where the energy and momentum exchange with the phonon gas can occur only through the mediation of the surface free-electron density, shows that the Debye-Waller exponent is directly proportional to the electron-phonon mass coupling constant λ. The comparison between the values of λ extracted from existing data on the Debye-Waller factor for various metal surfaces and the λ values known from literature indicates a substantial agreement, which opens the possibility of directly extracting the electron-phonon coupling strength in quasi-2D conducting systems from the temperature or incident energy dependence of the elastic helium atom scattering intensities.

Acoustic surface phonons of graphene on Ni(111)

The structure and the low-energy phonon dispersion of graphene (Gr) on Ni(111) have been experimentally investigated with helium atom scattering (HAS). The Rayleigh mode observed for Gr/Ni(111) is almost identical to the one measured on clean Ni(111). The energy of the flexural ZA mode at the Γ¯ point was found to be ∼20 meV, significantly lower than the value predicted by recent DFT calculations. The HAS diffraction spectra reveal that the graphene layer has a three-fold symmetry, with a lattice constant a = (2.48 ± 0.02) Å and shows an effective step-defect scattering reduction when the Ni(111) is covered with a graphene sheet. Gr/Ni(111) surface is a very efficient and inert mirror for He atoms, with a specular reflectivity of ca. 20%. The predominant role of inelastic scattering in Gr/Ni(111) is revealed by analysis of the diffraction spectra background and Debye–Waller measurements.

Observation of Localized Vibrational Modes of Graphene Nanodomes by Inelastic Atom Scattering.

Inelastic helium atom scattering (HAS) is suitable to determine low-energy (few meV) vibrations spatially localized on structures in the nanometer range. This is illustrated for the nanodomes that appear often on graphene (Gr) epitaxially grown on single crystal metal surfaces. The nature of the inelastic losses observed in Gr/Ru(0001) and Gr/Cu/Ru(0001) has been clarified by intercalation of Cu below the Gr monolayer, which decouples the Gr layer from the Ru substrate and changes substantially the out-of-plane, flexural phonon dispersion of epitaxial Gr, while maintaining the nanodomes and their localized vibrations. He diffraction proves that the Cu-intercalated Gr layer is well ordered structurally, while scanning tunneling microscopy reveals the persistence of the (slightly modified) periodic array of Gr nanodomes. A simple model explains the order of magnitude of the energy losses associated with the Gr nanodomes and their size dependence. The dispersionless, low-energy phonon branches may radically alter the transport of heat in intercalated Gr.

Graphene on Ni(111): Electronic Corrugation and Dynamics from Helium Atom Scattering.

Using helium atom scattering, we have studied the structure and dynamics of a graphene layer prepared in situ on a Ni(111) surface. Graphene/Ni(111) exhibits a helium reflectivity of ∼20% for a thermal helium atom beam and a particularly small surface electron density corrugation ((0.06 ± 0.02) Å peak to peak height). The Debye–Waller attenuation of the elastic diffraction peaks of graphene/Ni(111) and Ni(111) was measured at surface temperatures between 150 and 740 K. A surface Debye temperature of θD = (784 ± 14) K is determined for the graphene/Ni(111) system and θD = (388 ± 7) K for Ni(111), suggesting that the interlayer interaction between graphene and the Ni substrate is intermediary between those for strongly interacting systems like graphene/Ru(0001) and weakly interacting systems like graphene/Pt(111). In addition we present measurements of low frequency surface phonon modes on graphene/Ni(111) where the phonon modes of the Ni(111) substrate can be clearly observed. The similarity of these findings with the graphene/Ru(0001) system indicates that the bonding of graphene to a metal substrate alters the dynamic properties of the graphene surface strongly and is responsible for the high helium reflectivity of these systems.