Hydrogen-induced metallization of the 3C-SiC(0 0 1)-(3 × 2) surface

A surprising metallization of the SiC(0 0 1)-(3 × 2) surface induced by hydrogen adsorption was discovered in recent experiments. The effect was ascribed to dangling bonds created on the third layer of the surface system by H adsorption and stabilized by steric hindrance. We have investigated the surface metallization by density functional calculations. Our total-energy minimizations show that dangling bonds on the third layer are very unstable. Instead, H adatoms form angular Si-H-Si bonds on the third layer after the asymmetric dimers on the top layer have been saturated by H forming monohydrides. The novel Si-H-Si bonds on the third layer give rise to a metallic surface, indeed. But the mechanism for metallization is very different from the one suggested originally. Likewise, H atoms can also occupy bridge positions in angular Si-H-Si bonds on the second layer and induce metallization, as well. In addition to monohydrides on the top-layer dimers, we have also investigated dihydride surfaces with additional H on the second and/or third layer. The dihydride surface structure with H adsorbed on both the second and third layers is energetically most favorable and is also metallic. In all three cases the new Si-H-Si bonds are the origin of the surface metallization while its nature is somewhat more intricate, as will be discussed.     

The interaction of carbon with Si(1 1 1):As and Si(1 1 1):H surfaces, a theoretical study

Density functional theory calculations have been performed to determine the adsorption site of carbon at the Si(1 1 1):As and Si(1 1 1):H surfaces at different coverages. The As- and H-passivated surfaces were simulated by replacing the topmost Si layer by As or by saturating the Si dangling bonds with hydrogen atoms, respectively. Different high symmetry sites were considered. Carbon was placed successively in the fourfold (T₄) or threefold coordinated (H₃), the ontop (T₁) sites or substituted for a Si atom in the S₅ position located underneath the Si adatom in the T₄ site. We found that the preferred carbon adsorption site depends on the coverage of the passivated surfaces. At low coverages i.e. at 1/16 ML and 1/3 ML, it prefers a distorted T₄ position whereas at 1 ML, it occupies an H₃ site. This contrasts with the clean surface where the most energetically favored site is the S₅ at all coverages. Carbon adsorption induces a significant change in the structural geometry of the surface atoms, leading to a charge re-arrangement in the surface layers.     

Atomic and electronic structure of the Si(001) surface induced by hydrogen-adsorption

The initial stage of hydrogen (H) adsorption on the Si(001) surface is theoretically investigated to clarify the atomic and electronic structure induced by the adsorption. For this purpose, the electronic states are calculated in the density functional approach with the DV(discretized variation)-Xα-LCAO method. We also simulate the scanning tunneling microscopy (STM) image and the scanning tunneling spectroscopy (STS) spectrum in the first-principles approach. Our results of the STM image do not support the asymmetric dimer structure of the substrate with a H atom bonded to the upper Si atom. They conclude that the bright ball-like spot in the observed images comes from the free dangling bond induced on the remaining Si atom of the reacted dimer. However, the single particle picture cannot reproduce the observed features of the STS spectrum at the spot. We discuss that all the features can be well explained by the Coulomb blockade effect due to the electron correlation in the dangling bond state.     

Atomic wire oxidation of H-terminated Si(100)-( 2x1): domino reaction via oxidation and H migration

We studied oxidation at a dangling bond (DB) on the H-terminated Si(100) surface by the first-principles calculations. We found that oxidation easily occurs at the exposed DB on the H-terminated Si(100) surface. The dissociated O atoms are chemisorbed at a dimer bond and a back bond, resulting in adjacent H atom migration onto the DB. As a consequence of the alternate oxidation and subsequent H atom migration processes, the atomic wire oxidation is actually found to occur on the H-terminated Si(100) surface at low temperatures without desorbing H atoms, as observed in our scanning tunneling microscopy experiment.     

Structure Sensitive Reaction Channels of Molecular Hydrogen on Silicon Surfaces

The ability of the Si(001) surface to adsorb H2 molecules dissociatively increases by orders of magnitude when appropriate surface dangling bonds are terminated by H atoms. Through molecular beam techniques the energy dependent sticking probability at different adsorption sites on H-precovered and stepped surfaces is measured to obtain information about the barriers to adsorption, which decrease systematically with an increase in coadsorbed H atoms. With the help of density functional calculations for interdimer adsorption pathways, this effect is traced back to the electronic structure of the different adsorption sites and its interplay with local lattice distortions.     

Hydrogen chemisorption on the 100 (2 × 1) surfaces of Si and Ge

This paper combines a theoretical study of the Si(100) surface having a monolayer of atomic hydrogen chemisorbed to it with an experimental study of the analogous Ge(100) and Ge(110) surfaces. In the theoretical work the underlying (100) silicon surface is taken to be reconstructed according to the Schlier-Farnsworth-Levine pairing model with the hydrogen located on the unfilled tetrahedral bonds of this structure. Self-consistent calculations of the electronic potential, charge density, spectrum, and occupied surface density of states are carried out. The force on the hydrogen atoms is then calculated using the Hellman-Feynman theorem. This force is found to be close to zero, confirming that the hydrogen atoms are indeed at the equilibrium position for the chosen silicon geometry. Features in the calculated photoemission spectrum for the Si(100) 2 × 1 : H surface are discussed in terms of related features in the photoemission spectrum of Si(111) : H, but are found not to agree with the previously measured photoemission spectrum of Si(100) 2 × 1 : H. Measured photoemission and ion-neutralization spectra for Ge(100) 2 × 1 : H agree in their major features with what is calculated for Si(100) 2 × 1 : H, however, suggesting that the Ge(100) 2 × 1 : H surface is reconstricted according to the pairing model. Similarly, measured spectra for clean Ge(100) 2 × 1 agree with calculations for the row dimerized Si(100) surface.     

Room temperature hydrogenation of the Si(001)2 × 1 surface studied by angle-resolved electron energy loss spectroscopy

We observed the hydrogen adsorption on the Si(001)2 × 1 surface achieved at room temperature by angle-resolved electron energy loss spectroscopy (AR-ELS) and elastic low-energy electron diffraction. From measurements of the intensities of elastically diffracted beams, we found a characteristic hydrogen covered surface (called Si(001)2 × 1H(RT) surface in this paper), where all the diffracted beam intensities were enhanced drastically and a sharp 2 × 1 LEED pattern was observed. The angular dependence of the elastically diffracted beams on the 2 × 1H(RT) surface was different from that on the monohydride 2 × 1:H surface. On the 2 × 1H(RT) surface the S₃, transition from the back bond surface state disappeared in contrary to the 2 × 1:H surface and two hydrogen induced transitions were observed at 7.0 and 8.0 eV in AR-ELS spectra. We revealed that the 2 × 1H(RT) surface consisted of the monohydride and the dihydride phases with comparable weights. Additionally, we found the new transition S'₁, ascribed to the newly produced dangling bond surface state due to the rupture of the dimerization bond with hydrogen adsorption.     

Experimental and theoretical investigation of single Cu, Ag, and Au atoms adsorbed on Si(111)-(7x7)

Using scanning tunneling microscopy and first principles calculations, the adsorption sites of single Cu, Ag, and Au atoms on the Si(111)-(7x7) surface have been systematically investigated and identified. Despite their monovalence, these atoms were found to adsorb at high coordination sites, seeking to saturate the maximum number of dangling bonds. The stable adsorption sites were further observed to be distinctly different in the faulted and unfaulted half unit cells, showing an asymmetry that has never been observed for many other adsorbates.     

Initial Processes of Hydrogen Adsorption on Si（100） Surface

The adsorption of one monolayer H atoms on an ideal Si(100) surface is studied by using the self-consistent tight binding linear muffin-tin orbital method. Energies of adsorption systems of H atoms on different sites are calculated.It is found that the adsorbed H atoms are more favorable on B1 site (bridge site) with a distance 0.056 nm above the Si surface. There does not exist reaction barrier at the Si surface. The layer projected density states are calculated and compared with those of the clean surface. The charge transfers are also investigated.     

Initial Processes of Hydrogen Adsorption on Si(100) Surface

The adsorption of one monolayer H atoms on an ideal Si(100) surface is studied by using the self-consistent tight binding linear muffin-tin orbital method. Energies of adsorption systems of H atoms on different sites are calculated.It is found that the adsorbed H atoms are more favorable on B1 site (bridge site) with a distance 0.056 nm above the Si surface. There does not exist reaction barrier at the Si surface. The layer projected density states are calculated and compared with those of the clean surface. The charge transfers are also investigated.     

Probing the Si-Si dimer breaking of Si(100)2x1 surfaces upon molecule adsorption by optical spectroscopy

The adsorption of atoms and molecules of several gases of the Si(100)2x1 silicon reconstructed surface is investigated by surface differential reflectance spectroscopy. This UV-visible optical spectroscopy makes possible the discrimination between two adsorption modes, depending on whether or not the adsorption leads to breaking the Si-Si dimers. The observation of two different optical features is assigned to the bonding on dangling bonds or to the breaking of dimers, and gives access to the adsorption mode of hydrogen, water, oxygen, and pyridine. Moreover, the technique being quantitative, we can determine the total amount of dimers involved in the adsorption and monitor the adsorption kinetics.     

Chlorine adsorption on Si(1 1 1) studied by optical methods

The adsorption process of chlorine on Si(1 1 1) has been studied by means of real time surface differential reflectance (SDR) spectroscopy and second harmonic generation (SHG). The structure observed at 3.6 eV in SDR spectra is attributed to transitions including Si–Cl antibonding states. However, the overall feature is due to the removal of the electronic states of the clean surface. Developments of adsorption on Si adatom dangling bonds and breaking of adatom back bonds are obtained from SDR spectra and second harmonic (SH) intensity. They are well fit by the solutions of the rate equations under the assumption of adsorption of atoms without migration, and the initial sticking probability on the dangling bonds and the initial breaking probability of the back bonds are determined. Dependence of the adsorption kinetics on the carrier concentration is briefly reported.     

Oxidation of step edges on Si(001)-c(4x2)

The initial oxidation process of the ultraclean Si(001)-c(4x2) surface is studied using scanning tunneling microscopy at low temperature. At the early stage of oxygen adsorption, reactions with Si atoms at SB steps are dominant over those at terraces by more than 2 orders of magnitude, and they proceed in two distinct stages to high oxidation states. Guided by the ab initio calculations, the oxidation structures at each stage are proposed. The extreme reactivity of the step edge is due to the presence of rebonded adatoms with dangling bonds and weak rebonds, and their proximity allows the formation of -Si-O- chain structures along the step edge, unlike those on the Si(111) surface.     

SrO/Si(100)表面去氧过程的研究

借助高温扫描隧道显微镜和光电子能谱技术,深入研究了SrO/Si(100)表面向Sr/Si(100)再构表面的动态转化过程.Sr/Si(100)再构表面在硅基氧化物外延生长中起重要作用.在该动态转化过程中,样品在500 ℃的退火温度下,表面出现SrO晶化的现象;在550—590 ℃的退火温度下,SrO/Si(100)开始向Sr/Si(100)转化,界面和表面上的氧以气态的SiO溢出,使得表面出现大量凹槽状缺陷.并且在此动态转化过程中表面的电子态表现出金属特性,这是由于表层硅原子发生断键重排,从而在表面出现悬 关键词： SrO/Si表面 Sr/Si表面 扫描隧道显微镜 去氧过程     

First-principles study of atomic hydrogen adsorption on Fe3O4(100)

The adsorption of atomic hydrogen on an Fe₃O₄(100) surface is investigated using first-principles calculations. Our calculations reveal that hydrogen atoms prefer bonding with surface oxygen atoms not with tetrahedral iron atoms. The hydrogen-adsorbed Fe₃O₄(100) surface can be represented by a (1 × 1) unit cell, which is consistent with our recent experimental result. The spin-up surface-state bands are found to be shifted toward the deep level due to hydrogen adsorption. As a result, a band gap appears in the spin-up electronic states and half-metal behavior occurs at the H/Fe₃O₄(100) surface. The transition from a metallic to half-metallic surface due to hydrogen adsorption is discussed through analysis of the calculated spin-resolved band structure and differential charge density distribution. The reason for the enhancement of the spin polarization is attributed to a donation-redistribution process by O―H bond formation but not to detailed atomic structures of Fe and O atoms such like Jahn–Teller distortion.     

Doping and STM tip-induced changes to single dangling bonds on Si(0 0 1)

We have studied single Si dangling bonds on the Si(0 0 1) surface using scanning tunnelling microscopy (STM) and density functional theory (DFT) calculations. The Si dangling bonds are created by the chemisorption of single hydrogen atoms forming a Si-Si-H hemihydride. At room temperature, the hemihydride induces static buckling on adjacent Si-Si dimers. In the STM measurements, we observe that the orientation of the static buckling pattern can be reversed with tip-sample bias and influenced by the substrate doping. Our DFT calculations yield a correlation between the electron occupancy of the hemihydride Si dangling bond and the buckling orientation around it.     

Passivation effects of phosphorus on 4H-SiC(0001) Si dangling bonds: A first-principles study

The effect of phosphorus passivation on 4H-SiC(0001) silicon(Si) dangling bonds is investigated using ab initio atomistic thermodynamic calculations. Phosphorus passivation commences with chemisorption of phosphorus atoms at high-symmetry coordinated sites. To determine the most stable structure during the passivation process of phosphorus, a surface phase diagram of phosphorus adsorption on SiC(0001) surface is constructed over a coverage range of 1/9–1 monolayer(ML). The calculated results indicate that the 1/3 ML configuration is most energetically favorable in a reasonable environment. At this coverage, the total electron density of states demonstrates that phosphorus may effectively reduce the interface state density near the conduction band by removing 4H-SiC(0001) Si dangling bonds. It provides an atomic level insight into how phosphorus is able to reduce the near interface traps.     

Optical second-harmonic generation study of incorporation of nitrogen atoms at Si(1 0 0) surfaces

The kinetics of N incorporation into Si layers has been studied on the Si(1 0 0) surface probing surface dangling bonds with an optical second-harmonic (SH) generation during surface exposure to N atoms generated by a radio frequency N₂ plasma. It is observed that SH intensity decreases with N dose. The rate of decrease in SH intensity apparently decreases with surface temperature, whereas total amount of N atoms taken on the surface remains constant. This fact suggests that N atoms are incorporated at the subsurface layers at higher temperatures. It is shown that the N incorporation at the subsurface layers proceeds by the indiffusion of N atoms either directly or indirectly via intermediate, metastable adsorption at the first surface layer. Applying Kisliuk adsorption model, activation energies of the N indiffusion are evaluated to be 0.30 ± 0.03 and 0.34 ± 0.05 eV for the indirect and direct path, respectively.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

Chemisorption of isolated Br atoms on Si(100)-(2 × 1) studied by PAC

Chemisorption and desorption of isolated bromine adatoms on the Si(100)-(2 × 1) surface were investigated with nuclear methods. Br adsorption sites at low coverages of 10⁻³ monolayers (ML) were characterised by measuring the nuclear quadrupole interaction with perturbed γγ-angular correlation (PAC) of ⁷⁷Br→⁷⁷Se probe atoms. Below room temperature, two distinct adsorption sites for Br are revealed by PAC. One of them disappears after isochronal annealing above 300 K. The more stable probe-atom state is associated with single Br atoms saturating a dangling bond of the surface, while the less stable state is attributed to adsorption of Br at a bridge site. The potential barrier between the two adsorption sites is estimated to be 0.9(1) eV. At temperatures above 550 K, the fraction of atoms on distinct sites decreases, presumably due to surface diffusion. By measuring the γ-activity of the sample, complete desorption of the ⁷⁷Br atoms was observed above 620 K.