Experimental and theoretical study of rotationally inelastic diffraction of H2(D2) from methyl-terminated Si(111).

Fundamental details concerning the interaction between H2 and CH3-Si(111) have been elucidated by the combination of diffractive scattering experiments and electronic structure and scattering calculations. Rotationally inelastic diffraction (RID) of H2 and D2 from this model hydrocarbon-decorated semiconductor interface has been confirmed for the first time via both time-of-flight and diffraction measurements, with modest j = 0 → 2 RID intensities for H2 compared to the strong RID features observed for D2 over a large range of kinematic scattering conditions along two high-symmetry azimuthal directions. The Debye-Waller model was applied to the thermal attenuation of diffraction peaks, allowing for precise determination of the RID probabilities by accounting for incoherent motion of the CH3-Si(111) surface atoms.

Vibrational dynamics and band structure of methyl-terminated Ge(111).

A combined synthesis, experiment, and theory approach, using elastic and inelastic helium atom scattering along with ab initio density functional perturbation theory, has been used to investigate the vibrational dynamics and band structure of a recently synthesized organic-functionalized semiconductor interface. Specifically, the thermal properties and lattice dynamics of the underlying Ge(111) semiconductor crystal in the presence of a commensurate (1 × 1) methyl adlayer were defined for atomically flat methylated Ge(111) surfaces. The mean-square atomic displacements were evaluated by analysis of the thermal attenuation of the elastic He diffraction intensities using the Debye-Waller model, revealing an interface with hybrid characteristics.

The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1).

A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH3-Si(111)-(1 × 1) and CD3-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M̄-point and K̄-point.

Hybridization of surface waves with organic adlayer librations: a helium atom scattering and density functional perturbation theory study of methyl-Si(111).

The interplay of the librations of a covalently bound organic adlayer with the lattice waves of an underlying semiconductor surface was characterized using helium atom scattering in conjunction with analysis by density functional perturbation theory. The Rayleigh wave dispersion relation of CH3- and CD3-terminated Si(111) surfaces was probed across the entire surface Brillouin zone by the use of inelastic helium atom time-of-flight experiments. The experimentally determined Rayleigh wave dispersion relations were in agreement with those predicted by density functional perturbation theory.