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.     

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.     

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.     

Transition from overlayer growth to alloying growth of Ga on Si(111)-alpha-(sqrt[3]xsqrt[3])-Au

Atomic depth distribution and growth modes of Ga on an Si(111)-alpha-(sqrt[3]xsqrt[3])-Au surface at room temperature were studied after each monolayer deposition of Ga via reflection high-energy electron diffraction and characteristic x-ray spectroscopy measurements as functions of glancing angle theta(g) of the incident electron beam. One monolayer of Ga grew on the Au layer, and the sqrt[3]xsqrt[3] periodicity was conserved below the Ga overlayer. Above a critical Ga coverage of about one monolayer, this growth mode drastically changed; i.e., Au atoms dissociated from the sqrt[3]xsqrt[3] structure and Ga grew into islands of Ga-Au alloy.     

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.     

Disproportionation phenomena on free and strained Sn/Ge(111) and Sn/Si(111) surfaces

Distortions of the sqrt[3]x sqrt[3] Sn/Ge(111) and Sn/Si(111) surfaces are shown to reflect a disproportionation of an integer pseudocharge, Q, related to the surface band occupancy. A novel understanding of the (3 x 3)-1U ("1 up, 2 down") and 2U ("2 up, 1 down") distortions of Sn/Ge(111) is obtained by a theoretical study of the phase diagram under strain. Positive strain keeps the unstrained value Q=3 but removes distortions. Negative strain attracts pseudocharge from the valence band causing first a (3 x 3)-2U distortion (Q=4) on both Sn/Ge and Sn/Si, and eventually a (sqrt[3] x sqrt[3])-3U ("all up") state with Q=6. The possibility of a fluctuating phase in unstrained Sn/Si(111) is discussed.     

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.     

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.     

Evidence for the formation of different energetically similar atomic structures in Ag(111)-(square root[7] x square root[7])-R19.1 degrees-CH3S

The atomic structure and thermodynamic stability of Ag(111)(sqrt[7]xsqrt[7])-R19.1 degrees -CH3S has been studied by means of density functional calculations and atomistic first principles thermodynamics. The unreconstructed model and two recently proposed reconstructions have been considered. It is found that, in spite of significant differences in the atomic structure, the different surface models have a very similar surface free energy. It is claimed that the different ordered phases can coexist and that the appearance of one or another depends on the external preparation conditions.     

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.     

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).     

$\mathsf{\sqrt{3}}$ linear structures in the Te/Ni(111) system

Surface structures in the Te/Ni(111) system are revealed by using reflection high-energy electron diffraction combined with X-ray and ultraviolet photoelectron spectroscopies. At a 0.33 mono-layer (ML)-Te/Ni(111) surface, a reversible structural phase transition is observed with a transition temperature T_c of 380 C. The diffraction pattern from the low temperature phase is accompanied by streaks. The high and low temperature phases are characterized by and rectangle, respectively. The mechanism of the phase transition is explained by the order-disorder transition with a rumpled chain model. Both 0.51 ML- and 0.44 ML-Te/Ni(111) surfaces exhibit the complex diffraction patterns accompanied by diffuse streaks. These surface structures are characterized by the rectangle and , respectively. All diffuse streaks obtained at the above surfaces are consistently interpreted in the view of the ill-ordered arrangements of the well-ordered linear chains. It is shown that the linear structure is the key in the Te/Ni(111) system.Received: 1 December 2003, Published online: 20 April 2004PACS: 61.14.Hg Low-energy electron diffraction (LEED) and reflection high-energy electron diffraction (RHEED) - 68.65.-k Low-dimensional, mesoscopic, and nanoscale systems: structure and nonelectronic properties - 64.60.Cn Order-disorder transformations; statistical mechanics of model systems     

Direct observation of a (3 x 3) phase in alpha-Pb/Ge(111) at 10 K

We have investigated the recently reported structural phase transition at low temperature (LT) for alpha-Pb/Ge(111) [from a (3 x 3) symmetry to a disordered phase] using scanning tunneling microscopy (STM). By tracking exactly the same surface regions with atomic resolution while varying the sample temperature from 40 to 140 K, we have observed that substitutional point defects are not mobile, in clear contrast to previous assumptions. Moreover, STM data measured at the lowest temperatures ever reported for this system (10 K) show that while filled-state images display the apparent signature of a glassy phase with no long-range order, in empty-state images honeycomb patterns with (3 x 3) periodicity, and not distinguishable from data measured at much higher temperatures, are clearly resolved. These new observations cast serious doubts on the nature and/or on the existence of a disordered phase at LT.     

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.     

Surface Reconstruction with a Fractional Hole: (sqrt[5] x sqrt[5])R26.6 degrees LaAlO3 (001)

The structure of the (sqrt[5] x sqrt[5])R26.6 degrees reconstruction of LaAlO3 (001) has been determined using transmission electron diffraction combined with direct methods. It has a lanthanum oxide termination with one lanthanum vacancy per surface unit cell. Density functional calculations indicate that charge compensation occurs by a fractional number of highly delocalized holes, and that the surface contains no oxygen vacancies and the holes are not filled with hydrogen. The reconstruction can be understood in terms of expulsion of the more electropositive cation from the surface and increased covalency.     

Intrinsic character of the (3 x 3) to (square root 3 x square root 3) phase transition in Pb/Si(111)

We have investigated the (3 x 3) to (square root 3 x square root 3) reversible phase transition in Pb/Si(111) by means of variable temperature scanning tunneling microscopy and density functional first-principles calculations. By tracking exactly the same regions of the surface with atomic resolution in a temperature range between 40 and 200 K, we have observed the phase transition in real time. The ability to prepare and track exceptionally large domains without defects has allowed us to detect the intrinsic character of the phase transition at temperatures around 86 K. This intrinsic character is in full agreement with our first-principles calculations. Moreover, our results show that the hypothesis that point defects play a fundamental role as the driving force, reported for similar systems, can be discarded for Pb/Si(111).     

Graphene on ordered Ni-alloy surfaces formed by metal (Sn,Al) intercalation between graphene/Ni(111)

Deposition and intercalation of Al and Sn on Ni(111) supported graphene is investigated by Auger electron spectroscopy, low energy electron diffraction, and scanning tunneling microscopy. Al intercalates at ~ 200 °C while Sn intercalates at ~ 350 °C, indicating that the intercalation process is element specific. Both Al and Sn alloy with the Ni-substrate at higher annealing temperatures and form ordered alloy surfaces and surface alloys, respectively. Sn forms a (√3 × √3) R30° surface alloy by substituting surface Ni-atoms with Sn and thus the alloy maintains the same good lattice match with graphene as for Ni(111). Both Sn and Al are interacting weakly with graphene and can therefore be used to decouple graphene from the strongly interacting Ni substrate.     

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)].     

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.