Study of the Si(111) 7 × 7 surface structure by alkali- metal adsorption

When alkali-metals such as Li, Na, K, Rb and Cs were adsorbed on clean Si(111) 7 × 7 surface at room temperature, the intensity distribution of the original 7 × 7 RHEED pattern changes gradually with the increase of alkali-metal adsorption, and at last a new superstructure with 7 × 7 periodicity, here named δ-7 × 7 structure, has been observed. This change at room temperature can be explained if the 7 × 7 structure is mostly made of displacement. The structure model estimated from the intensity distribution of the δ-7 × 7 pattern is the one that has one vacancy at the corners of the 7 × 7 unit mesh and relaxed surrounding atoms. The change of the 7 × 7 structure by alkali-metal adsorption to this model is naturally understood with our new model (1984). For all alkali metals, by adsorption at high temperature 3 × 1 superstructure has also been observed for the first time.     

Electronic properties of alkali metal/silicon interfaces: A new picture

Adsorption of Na and Cs on the Si(100)2 × 1 surface in the monolayer range is investigated by core level and valence band photoemission spectroscopy using synchrotron radiation. The alkali metals are found to induce an electronic interface state near the Fermi level while hybridization between alkali adsorbate “s” and silicon substrate “3p” valence electrons occurs. These results provide evidence that the alkali metal/silicon bonding is covalent. This covalent bond is weak and polarized while plasmon at the alkali metal core level indicates adsorbate rather than substrate metallization.     

Leed,aes and photoemission measurements of epitaxially grown GaAs(001), (111)A and (1̄1̄1̄)B surfaces and their behaviour upon cs adsorption

Epitaxially grown GaAs(001), (111) and (1?1?1?) surfaces and their behaviour on Cs adsorption are studied by LEED, AES and photoemission. Upon heat treatment the clean GaAs(001) surface shows all the structures of the As-stabilized to the Ga-stabilized surface. By careful annealing it is also possible to obtain the As-stabilized surface from the Ga-stabilized surface, which must be due to the diffusion of As from the bulk to the surface. The As-stabilized surface can be recovered from the Ga-stabilized surface by treating the surface at 400°C in an AsH₃ atmosphere. The Cs coverage of all these surfaces is linear with the dosage and shows a sharp breakpoint at 5.3 × 10¹⁴ atoms cm^?2. The photoemission reaches a maximum precisely at the dosage of this break point for the GaAs(001) and GaAs(1?1?1?) surface, whereas for the GaAs(111) surface the maximum in the photoemission is reached at a higher dosage of 6.5 × 10¹⁴ atoms cm^?2. The maximum photoemission from all surfaces is in the order of 50μA Im^?1 for white light (T = 2850 K). LEED measurements show that Cs adsorbs as an amorphous layer on these surfaces at room temperature. Heat treatment of the Cs-activated GaAs (001) surface shows a stability region of 4.7 × 10¹⁴ atoms cm^?2 at 260dgC and one of 2.7 × 10¹⁴ atoms cm^?2 at 340°C without any ordering of the Cs atoms. Heat treatment of the Cs-activated GaAs(111) crystal shows a gradual desorption of Cs up to a coverage of 1 × 10¹⁴ atoms cm^?2, which is stable at 360°C and where LEED shows the formation of the GaAs(111) (√7 × √7)Cs structure. Heat treatment of the Cs-activated GaAs(1?1?1?) crystal shows a stability region at 260°C with a coverage of 3.8 × 10¹⁴ atoms cm^?2 with ordering of the Cs atoms in a GaAs(1?1?1?) (4 × 4)Cs structure and at 340°C a further stability region with a coverage of 1 × 10¹⁴ at cm^?2 with the formation of a GaAs(1?1?1?) (√21 × √21)Cs structure. Possible models of the GaAs(1?1?1?) (4 × 4)Cs, GaAs(1?1?1?)(√21 × √21)Cs and GaAs(111) (√7 × √7)Cs structures are given.     

Secondary ion emission processes of sputtered alkali ions from alkali/Si(100) and Si(111)

The secondary alkali ion yield vs. the work function change (Δφ) of Na, K and Cs/Si(100) and Si(111) was measured to discuss the details of secondary ion emission processes. In the case of alkali/metal systems, the secondary ion emission is explained by the electron tunneling model. In this model, the ionization of the ejected atom occurs as a result of electron resonant tunneling through the potential barrier separating an atom and a metal, and the secondary ion yield depends on exponentially the work function change of metal surface. For alkali/Si(100) systems, the secondary ion emission processes are explained in terms of the electron tunneling model since the secondary alkali ion yield vs. the work function change (Δφ) follows the exponential manner. However, it is not easy to apply the simple electron tunneling model to our experimental results for alkali/Si(111) systems. There is the essential difference in surface structures between Si(100) and Si(111). Therefore, it is suggested that the local electronic environment around the adsorbates might be taken into consideration for alkali/Si(111) systems.     

Second-harmonic generation spectroscopy on quantum wells: Au on Si(111)

×):Au-structure prior to film growth leads to increased amplitude in the oscillations indicating improved growth characteristics compared to the 7×7 substrate. The position of the maxima shifts towards lower coverage and the oscillation period decreases with increasing pump frequency. This behaviour is an unambiguous signature of quantum well resonances and, hence, clearly demonstrates that Au deposition on Si(111)(×):Au leads to well-defined quantum well structures with atomically flat interfaces. Furthermore, the rotationally anisotropic contribution to SHG also shows coverage oscillations as a result of quantum well effects and demonstrates the presence of structural order. Received: 12 October 1998     

Effect of surface reconstruction on the adsorption of Ge on clean Si(111)

The effect of ultrahigh vacuum deposition of Ge below and at monolayer (ML) coverage onto a 7 × 7 reconstructed clean Si(111) surface held at room temperature is studied by low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and photoemission yield spectroscopy (PYS). The results are compared to those obtained on 2 × 1 reconstructed clean Si(111) : (i) the Si dangling bond states are replaced by Ge dangling bond states at submonolayer coverages in both cases; (ii) the 7 × 7 reconstruction persists below 1 ML, it is not replaced by a ? 3 × ? 3 R30° at 1/3ML as it was on the 2 × 1; and (iii) the coverage below 1 ML is not homogeneous on the 7 × 7 reconstruction. This behaviour can be explained by the influence of the inhomogeneties associated with the 7 × 7 reconstruction.     

Crossover between monopole and multipole plasmon of Cs monolayers on Si(111) individually resolved in energy and momentum

The evolution of the plasmon spectrum of the Si(111) (7 x 7)-Cs surface has been studied by energy loss spectroscopy individually resolved in energy and momentum during the transition from substrate to Cs overlayer metallization. The multipole plasmon is identified by an extremely narrow angular distribution of the inelastic electron scattering, unaccounted for by standard dipole scattering theory. A crossover between multipole and monopole surface plasmon is observed at finite surface wave vectors , depending on Cs coverage, and reveals a high sensitivity of the short-wavelength multipole components on surface morphology.     

Atomic structure of Cs grown on Si(0 0 1)(2×1) surface by coaxial impact collision ion scattering spectroscopy

The atomic structure and the saturation coverage of Cs on the Si(0 0 1)(2×1) surface at room temperature have been studied by coaxial impact collision ion scattering spectroscopy (CAICISS). For the atomic structure of saturated Cs/Si(0 0 1)(2×1) surface, it is found that Cs atoms occupy a single adsorption site at T3 on the Si(0 0 1) surface. The height of Cs atoms adsorbed at T3 site is 3.18±0.05 Å from the second layer of Si(0 0 1)(2×1) surface. The saturation coverage estimated from the measured CAICISS intensity ratio and the proposed atomic structure is found to be 0.46±0.06 ML.     

Destruction and appearance of surface metallization in the system K/Si(111) 7×37

Qualitative changes are observed in the character of the surface electronic structure accompanying the adsorption of potassium on a Si(111) 7×7 surface. The metallic conductivity of the Si(111)7×7 surface is destroyed at the very early stages of adsorption. A new band induced by the adsorption of potassium is observed below the Fermi level. It is found that the K/Si(111)7×7 interface is semiconducting right up to saturating coverage. A surface transition from an insulating into a metallic state, accompanied by pinning of the Fermi level, is observed in the region of saturating coverage. Metallic conductivity arises in the adsorbed potassium layer as a result of the development of an induced surface band at the Fermi level. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 1, 27–30 (10 July 1997)     

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.     

Observation of methoxy species on the Si(111)(7 × 7) surface — A vibrational study

Chemisorption of methanol on the Si(111)(7 × 7) surface has been studied at ～ 300 K using high-resolution electron energy loss spectroscopy. Methanol reacts with the Si(111) surface to form the stable surface species SiOCH₃ and SiH. The methoxy species (CH₃O) is bonded to the Si surface with a covalent bond formed between its oxygen end and the dangling bond of the Si(111) surface atom. A structural model for methanol chemisorbed on the Si(111) surface is proposed.     

Rare gas coadsorption with Cs or K on Ag(111)

Rare gas (RG) coadsorption with submonolayer amounts of Cs or K on Ag(111) was studied using low-energy electron diffraction (LEED). A crossover in the alkali-RG interaction from repulsive to attractive was observed as a function of alkali species and of alkali coverage. The K---RG interaction was observed to be repulsive at all coverages, while the Cs---RG interaction was observed to be attractive at low Cs coverages and apparently repulsive at high Cs coverages. For the K + RG adsorption system, desorption data were analyzed to determine the spreading pressure in the alkali layer, thus showing that RG can be used as a 2D manometer in some coadsorption systems. From the spreading pressure it is possible to obtain some information about the properties of the adsorbed alkali such as the energy differences between commensurate and incommensurate phases. We also demonstrate that work function measurements from such coadsorption systems do not necessarily have a simple interpretation.     

Structural analysis of Si(111)-√21 × √21-(Ag,Cs) surface by reflection high-energy positron diffraction

We have investigated the Si(111)-√21 × √21-(Ag, Cs) superstructure using reflection high-energy positron diffraction. Rocking curve analysis based on the dynamical diffraction theory reveals that Cs atoms are located at a height of 3.04 Å above the underlying √3 × √3-Ag structure and that they form a triangular structure with a side length of 10.12 Å. The structure of the Si(111)-√21 × √21-(Ag, Cs) surface is significantly different from those of the Si(111)-√21 × √21-Ag and Si(111)-√21 × √21-(Ag, Au) surfaces, probably because of the different electronic structures of the alkali and noble metal atoms.     

Quasiparticle spectrum and optical excitations of semiconductor surfaces

I investigated the spectra of well-ordered semiconductor surfaces within an ab-initio framework. Both the quasi-particle spectrum of electron and hole states and the optical differential reflectivity spectrum were addressed. As examples, I discuss the spectra of three surfaces: Si(111)-(2×1), hydrogenated H:Si(111)-(1×1), and Si adatom-terminated 6H-SiC(0001)-(×). I studied a number of physical features beyond the single-particle band-structure picture. In the case of Si(111)-(2×1), the dangling-bond surface states give rise to a surface exciton which dominates the differential reflectivity spectrum. In the case of 6H-SiC(0001)-(×), a Mott-Hubbard metal-insulator transition is observed. All calculations were performed within many-body perturbation theory, employing single- and two-particle Green functions. The solutions of the corresponding equations of motion yielded the observable excitations, i.e., single-particle electron and hole excitations, as well as bound and resonant electron-hole pair excitations. Received: 28 April 2000 / Accepted: 19 June 2000 / Published online: 7 March 2001     

Modifying Quantum Well States of Pb Thin Films via Interface Engineering

We demonstrate the importance of interface modification on improving electron confinement by preparing Pb quantum islands on Si（111） substrates with two different surface reconstructions, i.e., Si（111）-7 ×7 and Si（111）- Root3×Root3-Pb （hereafter, 7 ×7 and R3）. Characterization with scanning tunneling microscopy/spectroscopy shows that growing Pb films directly on a 7 × 7 surface will generate many interface defects, which makes the lifetime of quantum well states （QWSs） strongly dependent on surface locations. On the other hand, QWSs in Pb films on an R3 surface are well defined with small variations in linewidth on different surface locations and are much sharper than those on the 7 × 7 surface. We show that the enhancement in quantum confinement is primarily due to the reduced electron-defect scattering at the interface.     

Coadsorption of cesium and oxygen on Ni(100): II. Cesium enhanced chemisorption and oxidation

The effects of adsorbed Cs atoms on the chemisorption and oxidation of Ni(100) surfaces have been studied with low energy electron diffraction and work function measurements. In addition to the c(2×2) structure of O on clean Ni(100), the preadsorption of Cs caused the formation of a (3×3) and a c(4×2) structure. The experimental results suggest that these new structures were due to ordered arrays of chemisorbed O atoms underneath the Cs layer, with O densities higher than that of c(2×2). It is found that a Cs overlayer increased drastically the rate of O chemisorption and NiO formation. Depending on the initial Cs coverage, the NiO formed in the (100) and (111) crystallographic rientations. During the enhanced oxidation the Cs layer remained on top of the oxide.     

Partially dissociative adsorption of water vapor on the Si(111) (7×7) surface

High-resolution vibrational electron energy-loss spectra have been measured of the Si(111) (7×7) surface exposed to water vapor at 300 K. Direct experimental evidence is given that water adsorption on the Si(111) (7×7) surface is partially dissociative.     

低温下水汽在Si(111)7×7表面上的化学吸附

用ELS和XPS研究了低温下水汽在Si(111)7×7表面上的化学吸附及其随退火温度的变化。150K低温下水以解离形式吸附在Si(111)7×7表面。     

The GaP(001) surface and the adsorption of Cs

GaP(001) cleaned by argon-ion bombardment and annealed at 500°C showed the Ga-stabilized GaP(001)(4 × 2) structure. Only treatment in 10^?5 Torr PH₃ at 500°C gave the P-stabilized GaP(001)(1 × 2) structure. The AES peak ratio $\text{P}\text{Ga}$ is 2 for the (4 × 2) and 3.5 for the (1 × 2) structure. Cs adsorbs with a sticking probability of unity up to 5 × 10¹⁴ Cs atoms cm^?2 and a lower one at higher coverages. The photoemission measured with uv light of 3660 Å showed a maximum at the coverage of 5 × 10¹⁴ atoms cm^?2. Cs adsorbs amorphously at room temperature, but heat treatment gives ordered structures, which are thought to be reconstructed GaP(001) structures induced by Cs. The LEED patterns showed the GaP(001)(1 × 2) Cs structure formed at 180°C for 10 h with a Cs coverage of 5 × 10¹⁴ atoms cm^?2, the GaP(001)(1 × 4) Cs formed at 210°C for 10 hours with a Cs coverage of 2.7 × 10¹⁴ atoms cm^?2, the GaP(001)(7 × 1) and the high temperature GaP(001)(1 × 4), the latter two with very low Cs content. Desorption measurements show three stability regions: (a) between 25–150°C for coverages greater than 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.2 eV; (b) between 180–200°C with a coverage of 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.8 eV; (c) between 210–400°C with a coverage of 2.7 × 10¹⁴ atoms cm^?2, and an activation energy of 2.5 eV.     

CH3Cl adsorption on a Si(100)2 × 1 surface modified by alkali metal overlayer studied by soft X-ray photoemission using synchrotron radiation

We present the first study of the effect of an alkali metal overlayer on the adsorption of an organic molecule, methylchloride, on a Si(100)2 × 1 surface. In strong contrast to the behavior of molecular oxygen or nitrogen which were found to react with the silicon substrate, there was no significant interaction between methylchloride and silicon, rather, the formation of alkali-chlorine bonds was observed. Core level and valence band spectroscopies using synchrotron radiation were used to study these systems. Sodium was found to exhibit the strongest interaction with mehtylchloride which was dissociated, while the effects produced by K and Cs were weaker.