Structure dependent oxidation of clean Si(111) surfaces

The initial process of oxygen adsorption is investigated by high resolution photoemission yield spectroscopy on (2 × 1) and (7 × 7)Si(111) surfaces. The corresponding changes in work function, ionization energy and surface state distribution, within and close to the gap, depend strongly on the initial structure. It is shown for the first time that, after completion of a “monolayer” of oxygen, the dangling bond states completely disappear on the (7 × 7) structure while a few percents remain unaffected on the (2 × 1).     

Comparison of the Si(111) (7 × 7) and (1×1)surfaces

High-resolution electron energy-loss spectroscopy and monochromatic low-energy electron diffraction have been applied to the study of the Si(111)(7 × 7) surface and the thermally-quenched Si(111) (1 × 1) surface. For the (1 × 1) surface, the inelastic continuum, observed for the (7 × 7) surface, due to the Drude absorption of electrons in the dangling-bond surface states is not existent, which indicates that the surface-state band associated with the dangling-bonds of the (1 × 1) surface is insulating. The observed electronic transitions indicate that the (7 × 7) and (1 × 1) surfaces have similar local band geometries and that they differ only in long-range order. The (1 × 1) surface is considered to have a disordered structure. The defect model is favored for the (7 × 7) structure.     

Structural analogy between GeSi(111)-5 × 5 and Si(111)-7 × 7 surfaces

Low energy electron diffraction (LEED) patterns for the GeSi(111)-5 × 5 surface are reported and compared to those for the Si(111)-7 × 7 surface. Parallels between the observed LEED patterns are explained by a structural analogy between GeSi(111)-5 × 5 and Si(111)-7 × 7 surfaces. Both the (5 × 5) and (7 × 7) patterns are shown to be consistent with structural models of the triangle-dimer type previously proposed for Si(111)-7 × 7 surface.     

Electronic structure of Si(111) surfaces

We report on new angle-resolved photoemission studies of Si(111) 2 × 1 and 7 × 7 surfaces. The emission from the 2 × 1 surface shows much structure. For normal emission the energy positions are insensitive to the photon energy in the range 19–27 eV. The emission has been interpreted as a probe of the surface density of states, SDOS, including both surface states, resonances and bulk-like states. The SDOS was also calculated as a function of parallel momentum k_∥ for a model of the Si(111) 2 × 1 surface obtained from energy minimization considerations. We identify emission from the dangling bond band, which has a positive dispersion of 0.6 eV, and also emission from surface resonances which have some character of the compressed and stretched back bonds. There are also other predicted surface resonances that correspond to experimental peaks which have not been identified in previous work. Except for the dangling bond band, the surface resonances are limited in k_∥ space, so that it is not possible to follow these resonance bands over all angles. Maximum intensity for the normal emission from the dangling bond is obtained at 23 eV, while the emission from the lowest s-like states monotonically increases towards 30 eV photon energy. When annealing the cleaved 2 × 1 surface to the 7 × 7 reconstructed surface, the spectra broaden significantly. The intensity of the dangling bond decreases and we see a very small metallic edge.     

On the structure of the laser irradiated Si(111)-(1 × 1) surface

We have studied the geometric structure of the Si(111)-(1 × 1) surface, prepared from a Si(111)-(7 × 7) surface with a pulsed ruby laser. With the technique of medium energy ion scattering, in combination with channeling and blocking, we find that this surface has a structure very similar to the (7 × 7) surface. Our results are inconsistent with a simple relaxation model.     

Angle-resolved ultraviolet photoemission study of Si(111) 7 × 7 and 1 × 1 surfaces

Angle-resolved ultraviolet photoelectron spectra of Si(111) 7 × 7 and 1 × 1 surfaces have been measured as a function of temperature from ambient temperature to ≈ 1120°C. Both the Si(111) 7 × 7 and 1 × 1 surfaces show obvious surface metallic edge at all the temperatures. A middle peak among three surface-state peaks observed for ambient-temperature 7 × 7 surface has been found to disappear for high-temperature 7 × 7 surface. In going from high-T 7 × 7 surface to high-T 1 × 1 surface, no essential changes in the surface-state peaks have been found to occur.     

Dangling bond surface state of Si(111): New results

By angle resolved photoemission on Si(111) 2 × 1 surfaces, the main surface structure at ?0.85 eV below E_F is shown to exhibit a strong s?p_z character in contradiction with previous measurements. The similarity of the results on the 2 × 1 and 7 × 7 surfaces, together with theoretical calculations lead us to favor a buckled model for the 2 × 1 surface and a model based on ring like arrangements of lowered and raised atoms for the 7 × 7 surface.     

Si(113)表面原子结构的低能电子衍射研究

利用低能电子衍射(LEED)研究了离子轰击加退火处理的和淀积外延的两种Si(113)表面的原子结构。发现对于经750—800℃退火后的两种Si(113)表面,当其温度高于600℃时存在1×1非再构表面相。随着样品温度缓慢地冷却至室温,Si(113)-1×1表面经过3×1(约600—400℃)最后转变为3×2再构。当退火温度为600℃时,则只出现3×1再构,室温下的3×2和3×1表面都是很稳定的。讨论了表面杂质对Si(113)表面原子结构的影响。在衬底温度为580℃的Si(113)表面上进行淀积生长,当外延 关键词：     

Hydrogen adsorption and surface structures of silicon

The adsorption of atomic hydrogen on silicon (111)2 × 1 cleaved, (111) 7 × 7, and (100) 2 × 1 surfaces has been studied by using electron energy loss spectrscopy (ELS) and Photoemission spectroscopy (UPS). On all surfaces the hydrogen removes the “dangling bond” surface state and a new peak in the density of states at lower energies corresponding to the SiH bond is found. The LEED pattern of the equilibrium surfaces (111) 7 × 7 and (100) 2 × 1 is not altered by hydrogen adsorption, while on the cleaved (111) 2 × 1 surface the fractional order spots are extinguished. The Haneman surface-buckling model therefore provides an explanation for the surface reconstruction of the cleaved (111) 2 × 1 surfaces. For the equilibrium surfaces, (111) 7 × 7 and the (100) 2 × 1, the data are consistent with the Lander-Phillips model.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Surface phase transitions and defect-phonon interactions: The Si(111)-(2 × 1) to (7 × 7) to (1 × 1) transitions

A thermodynamic equation is derived, showing the relation between defect-phonon interactions, the free energy of formation of defects and surface disordering or melting. When applied to Si(111), the theory shows that the (2 × 1) to (7 × 7) transition temperature is deduced from the (7 × 7) to (1 × 1) temperature via the relative concentrations of dangling bonds on the (2 × 1) and (7 × 7) surfaces.     

Translational heating of D(2) molecules thermally desorbed from Si(100) and Ge(100) surfaces

The translational energies of D(2) molecules thermally desorbed from the Si(100) and Ge(100) surfaces under a heating rate of 6 K/s have been measured. In contrast to the previous laser desorption study, results show a considerable translational heating; the observed translational temperature is about 3 times higher than the desorption temperature for both surfaces. This fact indicates that energy barriers for adsorption are present even in the desorption pathway. Detailed balance is applicable to the adsorption and desorption dynamics of hydrogen on the Si(100) surface.     

Reflectometric study of surface states and oxygen adsorption on clean Si(100) and (110) surfaces

External differential reflection measurements were carried out on clean Si(100) and (110) surfaces in the photon energy range of 1.0 to 3.0 eV at 300 and 80 K. The results for Si(100) at 300 K showed two peaks in the joint density of states curve, which sharpened at 80 K. One peak at 3.0 ± 0.2 eV can be attributed to optical transitions from a filled surface states band near the top of the valence band to empty bulk conduction band levels. The other peak at 1.60 ± 0.05 eV may be attributed to transitions to an empty surface states band in the energy gap. This result favours the asymmetric dimer model for the Si(100) surface. For the (110) surface at 300 K only one peak was found at 3.0 ± 0.2 eV. At 80 K the peak height diminished by a factor of two. Oxygen adsorption in the submonolayer region on the clean Si(100) surface appeared to proceed in a similar way as on the Si(111) 7 × 7 surface. For the Si(110) surface the kinetics of the adsorption process at 80 K deviated clearly. The binding state of oxygen on this surface at 80 K appeared to be different from that on the same surface at 300 K.     

Scanning tunneling microscope study of dynamic phenomena on clean Si(111) surfaces: Si magic clusters and their role

On Si(111) surfaces, we observed a special type of Si magic clusters with a variable-temperature scanning tunneling microscope (STM). At temperatures above 400°C, these clusters migrate on Si(111)-(7×7) surfaces as a whole. They can hop within a half-cell of Si(111)-(7×7), but sometimes they hop away from their original halves, leaving the 7×7 structure intact. When this happens, the magic cluster usually reappears at a site a few hundred Å away. We characterize its structure and derive path-specific hopping parameters using Arrhenius analysis. In the long hops, interestingly, magic clusters exhibit a strong bias for moving in the direction of the heating current. Effects of the directed motion in electromigration and those in thermal migration are determined separately and quantitatively. We also observed fluctuations of step edges through detachment and attachment of magic clusters. The filling of two-dimensional (2-D) craters and the decay of 2-D islands are also found to occur preferentially at the cathode side. These observations provide important clues for understanding the atomic processes in epitaxial growth and in electromigration on Si(111) surfaces. Based on our observations, the phase transition of 7×7↔1×1 is also discussed.     

Observation of Si(111) and gold-deposited Si(111) surfaces using micro-probe reflection high-energy electron diffraction

Observations of clean Si(111) and gold-deposited Si(111) surfaces have been performed using micro-probe reflection high-energy electron diffraction. It was found that many atomic steps on a Si(111) surface run in nearly the same direction, about 9° off the [1̄1̄2] direction. When gold was deposited on this surface at a substrate temperature of about 800°C, 5 × 1, diffuse √3 × √3R30°, sharp √3 × √3 R30° structures and Au clusters appeared on the surface with continuation of the deposition. During the deposition process, it was found that one kind of Si(111) 5 × 1 Au domain grew selectively along these atomic steps and nearly covered the entire surface. A phenomenon of gold clusters moving during the deposition was also observed. These clusters all moved in nearly the same direction so as to climb the atomic steps.     

Structure of Si(111)−7 × 7

A model of the Si(111)?7 × 7 surface atomic arrangement is put forward on the basis of results already established for Si(111) and Si(100) surfaces. The unit mesh contains a triangular double-layer island with 21 first-layer atoms. The island is laterally expanded and is bounded by [1̄1̄2] steps with second-layer edge atoms forming asymmetric dimers. It is shown that salient features of low energy electron diffraction (LEED) patterns for Si(111)?7 × 7 can be explained by the model. The LEED patterns are interpreted qualitatively by a double-diffraction mechanism involving forward diffraction in the selvedge. It is shown that the patterns contain characteristic formations of fractional-order spots attributable to the dimers at the island boundaries. The best agreement with observed patterns is obtained with the following parameter values: dimer bond length 2.5 ± 0.2 Å, island lateral expansion 3 ± 2%. Some of the implications of the model for the chemical reactivity and electronic properties of the Si(111)?7 × 7 surface are discussed.     

A leed-aes study of thin Pd films on Si(111) and (100) substrates

A system Pd (deposit)-Si (substrate) has been studied by LEED and AES. Pd₂Si formed on Si(111) became epitaxial after a short time of annealing at a temperature between 300 and 700°C, while the Pd₂Si formed on Si(100) did not, in both cases the surfaces of the Pd₂Si being covered with a very thin Si layer. A sequence of superstructures (3√3 × 3√3), (1 × 1), and (2√3 × 2√3) was observed successively in Pd/Si(111) as the annealing temperature was increased. A (√3 × √3) structure was obtained by sputtering the 3√3 surface slightly. It was found that the √3 structure corresponds to Pd²Si(0001)-(1 × 1) grown epitaxially on Si(111), and that the 3√3 structure comes from the thin Si layer accumulated over the silicide surface, while the 2√3 and 1 structures arise from a submonolayer of Pd adsorbed on Si(111). Superstructures observed on a Pd/Si(100) system are also studied.     

Ⅶ族元素在Si(111)和Ge(111)表面上的吸附

本文用原子集团模型和电荷自洽的EHT方法研究了Ⅶ族元素在Si(111)和Ge(111)表面上的化学吸附。利用能量极小的原则确定了各元素的化学吸附构型。对于Cl,在这两个表面均是顶位吸附。对于Ⅰ,都呈三度空位吸附。对Br,顶位及三度空位吸附均能发生,但是在Si(111)表面顶位吸附要优于三度空位,而在Ge(111)表面则三度空位吸附优于顶位。最后对Ⅶ族元素原子在这两种表面的吸附行为作了讨论,并与实验作了比较。 关键词：     

Si(111)理想、弛豫及2×1重构表面的声子谱研究

本文利用微扰的方法考虑了占据态与空态间的耦合对能带能量的影响,给出延展键轨道近似下半导体力常数的解析表达式.利用这些表达式求出Si(111)的理想、1×1弛豫及2×1Haneman模型重构表面的声子色散曲线及其表面振动的振幅分布.不同表面结果的比较显示弛豫及重构对表面声子性质具有决定性的影响.同时,分析表明Haneman的2×1表面重构模型不足以满意地解释有关实验结果.     

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.