Surface soft phonon and the sqrt[3] x sqrt[3] <--> 3x3 phase transition in Sn/Ge(111) and Sn/Si(111)

Density functional theory calculations show that the reversible Sn/Ge(111) sqrt[3]xsqrt[3]<-->3x3 phase transition can be described in terms of a surface soft phonon. The isovalent Sn/Si(111) case does not display this transition since the sqrt[3]xsqrt[3] phase is the stable structure at low temperature, although it presents a partial softening of the 3x3 surface phonon. The rather flat energy surfaces for the atomic motion associated with this phonon mode in both cases explain the experimental similarities found at room temperature between these systems. The driving force underlying the sqrt[3]xsqrt[3]<-->3x3 phase transition is shown to be associated with the electronic energy gain due to the Sn dangling bond rehybridization.     

Determination of the Sn 4d line shape of the Sn/Ge(111) radical3 x radical3 and 3x3 surfaces

The Sn 4d line shapes of the Sn/Ge(111) sqrt[3]xsqrt[3] and 3x3 surfaces are currently under debate. By employing LEED, core-level, and valence band spectroscopy we have been able to determine the correct Sn 4d line shapes for these surfaces. Contrary to a recent study we conclude that the majority of the earlier reports present line shapes close to the correct ones. At 70 K we identify three 4d components in the 3x3 spectrum, two of which are identified with the two types of Sn atoms in the 3x3 cell. The third component is attributed to Sn atoms surrounding Ge substitutional defects.     

Phonon softening,chaotic motion,and order-disorder transition in Sn/Ge(111)

The phonon dynamics of the Sn/Ge(111) interface is studied using high-resolution helium atom scattering and first-principles calculations. At room temperature we observe a phonon softening at the Kmacr; point in the (sqrt[3]xsqrt[3])R30 degrees phase, associated with the stabilization of a (3x3) phase at low temperature. That phonon band is split into three branches in the (3x3) phase. We analyze the character of these phonons and find out that the low- and room-temperature modes are connected via a chaotic motion of the Sn atoms. The system is shown to present an order-disorder transition.     

Sn/Ge(111) surface charge-density-wave phase transition

Angle-resolved photoemission has been utilized to study the surface electronic structure of 1 / 3 monolayer of Sn on Ge(111) in both the room-temperature (sqrt[3]xsqrt[3] )R30 degrees phase and the low-temperature ( 3x3) charge-density-wave phase. The results reveal a gap opening around the ( 3x3) Brillouin zone boundary, suggesting a Peierls-like transition despite the well-documented lack of Fermi nesting. A highly sensitive electronic response to doping by intrinsic surface defects is the cause for this unusual behavior, and a detailed calculation illustrates the origin of the ( 3x3) symmetry.     

Triangular Mott-Hubbard insulator phases of Sn/Si(111) and Sn/Ge(111) surfaces

The ground state of Sn/Si(111) and Sn/Ge(111) surface alpha phases is reexamined theoretically, based on ab initio calculations where correlations are approximately included through the orbital dependence of the Coulomb interaction (in the local density+Hubbard U approximation). The effect of correlations is to destabilize the vertical buckling in Sn/Ge(111) and to make the surface magnetic, with a metal-insulator transition for both systems. This signals the onset of a stable narrow gap Mott-Hubbard insulating state, in agreement with very recent experiments. Antiferromagnetic exchange is proposed to be responsible for the observed Gamma-point photoemission intensity, as well as for the partial metallization observed above 60 K in Sn/Si(111). Extrinsic metallization of Sn/Si(111) by, e.g., alkali doping, could lead to a novel 2D triangular superconducting state of this and similar surfaces.     

Direct observation of sn adatoms dynamical fluctuations at the Sn/Ge(111) surface

The well-known low-temperature phase transition sqrt[3]xsqrt[3] to 3x3 for the 1/3 monolayer of Sn adatoms on the Ge(111) surface has been studied by scanning tunneling microscopy. The STM tip was used as a probe to record the tunneling current as a function of time on top of the Sn adatoms. The presence of steps on the current-time curves allowed the detection of fluctuating Sn atoms along the direction vertical to the substrate. We discuss the effect of temperature and surface defects on the frequency of the motion, finding consistency with the dynamical fluctuations model.     

Metallic nature of the alpha-Sn/Ge(111) surface down to 2.5 K

Low temperature (down to 2.5 K) scanning tunneling microscopy (STM) and spectroscopy (STS) measurements are presented to assess the nature of the alpha-Sn/Ge(111) surface. Bias-dependent STM and STS measurements have been used to demonstrate that such a surface preserves a metallic 3 x 3 reconstruction at very low temperature. A tip-surface interaction mechanism becomes active below about 20 K at the alpha-Sn/Ge(111) surface, resulting in an apparent unbuckled (sqrt[3] x sqrt[3]) reconstruction when filled states STM images are acquired with tunneling currents higher than 0.2 nA.     

Structural origin of the Sn 4d core level line shape in Sn/Ge(111)-(3x3)

High-resolution photoemission of the Sn 4d core level of Sn/Ge(111)-(3x3) resolves three main components in the line shape, which are assigned to each of the three Sn atoms that form the unit cell. The line shape found is in agreement with an initial state picture and supports that the two down atoms are inequivalent. In full agreement with these results, scanning tunnel microscopy images directly show that the two down atoms are at slightly different heights in most of the surface, giving rise to an inequivalent-down-atoms (3x3) structure. These results solve a long-standing controversy on the interpretation of the Sn 4d core-level line shape and the structure of Sn/Ge(111)-(3x3).     

Charge ordering induced by intrinsic defects in Sn/Ge(111) submonolayers with a coverage close to 1/3

A thermodynamic model is suggested for a (3×3)-type structure formation with a charge density wave (CDW) arising against the background of a \((\sqrt 3 \times \sqrt 3 )R30^\circ\)-type structure in a Group IV metal (Sn, Pb) submonolayer adsorbed with a coverage of ≈1/3 at the (Ge, Si) semiconductor (111) surface. Calculations are carried out by using a self-consistent theory for static fluctuations of the order parameter amplitude. It is shown that the low-symmetry (3×3) phase can nucleate at point defects of the submonolayer as charge-ordered areas of finite radius. The spatial configuration of the CDW and its temperature dependence are calculated. The results obtained are compared with the experimental data for the Sn/Ge(111) system.     

Novel electronically driven surface phase predicted in C/Si(111)

We predict a novel electronically driven phase for the recently created C/Si(111) surface at 1/3 monolayer coverage. Whereas the isoelectronic surface Sn/Ge(111) is a 3 x 3 distorted metal and Si/SiC(0001) is an undistorted magnetic Mott insulator, the new phase combines both features. Two of three adatoms in C/Si(111) should form a distorted (3 x 3) honeycomb sublattice, the third an undistorted insulating and magnetic triangular sublattice. The generally conflicting elements, namely, band energy, favoring distortion, and strong electron correlations favoring a Mott state, actually conspire in this case. This kind of state represents the surface analog of the Fazekas-Tosatti state in the charge density wave compound 1T-TaS2.     

A density-functional theory investigation on disorption of O2 on Sn(111) and its comparison with initial oxidation on the X(111) (X=Si,Ge, Sn,Pb) surfaces

The first-principles calculations are performed to investigate the adsorption of O₂ molecules on an Sn(111) 2×2 surface. The chemisorbed adsorption precursor states for O₂ are identified to be along the parallel and vertical channels, and the surface reconstructions of Sn(111) induced by oxygen adsorption are studied. Based on this, the adsorption behaviours of O₂ on X(111) (X=Si, Ge, Sn, Pb) surfaces are analysed, and the most stable adsorption channels of O₂ on X(111) (X=Si, Ge, Sn, Pb) are identified. The surface reconstructions and electron distributions along the most stable adsorption channels are discussed and compared. The results show that the O₂ adsorption ability declines gradually and the amount of charge transferred decreases with the enhancement of metallicity.     

Surface phase transitions induced by electron mediated adatom-adatom interaction

We propose that the indirect adatom-adatom interaction mediated by the conduction electrons of a metallic surface is responsible for the sqrt[3]xsqrt[3]<==>3x3 structural phase transitions observed in Sn/Ge (111) and Pb/Ge (111). When the indirect interaction overwhelms the local stress field imposed by the substrate registry, the system suffers a phonon instability, resulting in a structural phase transition in the adlayer. Our theory is capable of explaining all the salient features of the sqrt[3]xsqrt[3]<==>3x3 transitions observed in Sn/Ge (111) and Pb/Ge (111), and is in principle applicable to a wide class of systems whose surfaces are metallic before the transition.     

Low temperature disordered phase of alpha-Pb/Ge(111)

A new structural phase transition has been observed at low temperature for the one-third of a monolayer (alpha phase) of Pb on Ge(111) using a variable-temperature scanning tunneling microscope. The well-known (sqrt[3] x sqrt[3])R30 degrees to (3 x 3) transition is accompanied by a new structural phase transition from (3 x 3) to a disordered phase at approximately 76 K. The formation of this "glasslike" phase is a consequence of competing interactions on different length scales.     

Role of the Metal/Semiconductor interface in quantum size effects: Pb /Si(111)

Self-organized islands of uniform heights can form at low temperatures on metal/semiconductor systems as a result of quantum size effects, i.e., the occupation of discrete electron energy levels in the film. We compare the growth mode on two different substrates [Si(111)- (7x7) vs Si(111)- Pb(sqrt[3]xsqrt[3] )] with spot profile analysis low-energy electron diffraction. For the same growth conditions (of coverage and temperature) 7-step islands are the most stable islands on the (7x7) phase, while 5-step (but larger islands) are the most stable islands on the (sqrt[3]xsqrt[3] ). A theoretical calculation suggests that the height selection on the two interfaces can be attributed to the amount of charge transfer at the interface.     

Observation of a Mott insulating ground state for Sn/Ge(111) at low temperature

We report an investigation on the properties of 0.33 ML of Sn on Ge(111) at temperatures down to 5 K. Low-energy electron diffraction and scanning tunneling microscopy show that the (3x3) phase formed at approximately 200 K, reverts to a new ((square root 3)x(square root 3))R30 degrees phase below 30 K. The vertical distortion characteristic of the (3x3) phase is lost across the phase transition, which is fully reversible. Angle-resolved photoemission experiments show that, concomitantly with the structural phase transition, a metal-insulator phase transition takes place. The ((square root 3)x(square root 3))R30 degrees ground state is interpreted as the formation of a Mott insulator for a narrow half-filled band in a two-dimensional triangular lattice.     

Effect of adsorbed Sn on Ge diffusivity on Si(111) surface

The effect of adsorbed Sn as a surfactant on Ge diffusion on a Si(111) surface has been studied by Low Energy Electron Diffraction and Auger Electron Spectroscopy. The experimental dependence of Ge diffusion coefficients on the Si(111) surface versus temperature in the presence of adsorbed Sn atoms has been measured in the range from 300 to 650°C. It has been shown that at a Sn coverage of about 1 monolayer the mobility of Ge atoms increases by several orders of magnitude.      

Evidence of Sn adatoms quantum tunneling at the alpha-Sn/Si(111) surface

We present a low-temperature scanning tunneling microscopy study of the alpha-Sn/Si(111) surface that demonstrates the fluctuating behavior of the Sn adatoms. The dynamical fluctuation model, successfully applied in describing the alpha-Sn/Ge(111) surface, is proposed for the related alpha-Sn/Si(111) surface too, although with a much lower transition temperature. In addition, a new phenomenon appears responsible for the unexpected evidence that the average oscillation frequency remains constant at temperatures lower than 15 K, in contradiction to the Arrhenius law. We explain this phenomenon as quantum tunneling of Sn adatoms.     

Alignment of Ge nanoislands on Si(111) by Ga-induced substrate self-patterning

A novel mechanism is described which enables the selective formation of three-dimensional Ge islands. Submonolayer adsorption of Ga on Si(111) at high temperature leads to a self-organized two-dimensional pattern formation by separation of the 7 x 7 substrate and Ga/Si(111)-(square root[3] x square root[3])-R30 degrees domains. The latter evolve at step edges and domain boundaries of the initial substrate reconstruction. Subsequent Ge deposition results in the growth of 3D islands which are aligned at the boundaries between bare and Ga-covered domains. This result is explained in terms of preferential nucleation conditions due to a modulation of the surface chemical potential.     

Insulating ground state of Sn/Si(111)-(square root 3 x square root 3)R30 degrees

The Sn/Si(111)-(square root 3 x square root 3)R30 degrees surface was so far believed to be metallic according to the electron counting argument. We show, by using tunneling spectroscopy, scanning tunneling microscopy, photoemission, and photoelectron diffraction, that below 70 K this surface has a very low density of states at the Fermi level and is not appreciably distorted. The experimental results are compatible with the insulating Mott-Hubbard ground state predicted by LSDA+U calculations [G. Profeta and E. Tosatti, Phys. Rev. Lett. 98, 086401 (2007)].     

Hole effective mass in strained Si (111)

The directional, averaged, and density-of-states effective masses of holes have been calculated for strained Si/(111)Si1-xGex. The results for the directional effective mass show that the effect of strain makes the constant energy surface of heavy holes more obvious warping than that in relaxed Si. The [111] and [110] directional effective masses of heavy holes decrease significantly under strain. It is found that the averaged effective mass of heavy holes decreases with increasing Ge fraction, while that o...