Hydrogen on Si: Ubiquitous surface termination after wet-chemical processing

The manufacture of microelectronic devices based on silicon technology is largely dominated by wet chemical processes. By ultraclean sample preparation in air and a fast transfer into UltraHigh Vacuum (UHV) we open up a way for the atomic-scale structural and chemical characterization of silicon surfaces immediately after wet-chemical processing. Using Scanning Tunneling Microscopy (STM), ThermoDesorption (TDS) and InfraRed Spectroscopy (IRS), we find that a surface termination predominantly by hydrogen results from all the different wet-chemical treatments investigated (etching with hydrofluoric acid, rinsing with hot water, chemomechanical polishing)-despite the different chemical ambients and process parameters involved. Microscopically, a crystallographically preferential attack of the silicon is observed in all these processes which results, to a different extent, in anisotropic defect structures on the surfaces. This is explained by an interplay of aqueous reaction kinetics and sterical hindrance on the silicon surface. It is pointed out how a UHV surface analysis of the micromorphology of wet-chemically treated silicon surfaces, so far carried out mostly on Si(111) due to its easier preparation and experimental accessability, may help to provide the in-depth understanding of the atomic-scale mechanisms during wet-chemical processing demanded by the progressing miniaturization of microelectronic devices. The atomically smoother and chemically more homogeneous Si(111) obtained after preferential etching with NH₄F suggests that in future applications Si(111) may gain importance over Si(100), which still dominates in today's semiconductor technology, since future devices increasingly rely on tailor-made and ideal properties on an atomic scale. Due to their structural and chemical simplicity and well-controlable characteristics, H-teminated surfaces after wet-chemical preparation also form ideal substrates for conventional UHV surface studies such as absorption and MBE-growth experiments.     

Plasma deposition of hydrogenated amorphous silicon: Studies of the growth surface

This review focusses on the plasma-surface interactions and surface processes involved in a-Si: H thin film growth. We restrict our discussion of growth fluxes to a summary, and do not address plasma kinetics. In recent years, powerful in situ experiments have been carried out on the growing film surface, which reveal the adsorption, penetration, reaction, and elimination of precursor species, as well as the atomic-scale morphology and composition of the growth zone. Good data sets are available both for PACVD and reactive magnetron sputter deposition. These form an interesting comparison, since the former process is dominated by the hydrogen-rich radical SiH₃ at low energy, and the latter by energetic atomic Si and H. We review the key experiments and conclusions, underlining those aspects which are well established and those which remain qualitative; and we discuss the transition from amorphous to fine-grained polycrystalline film growth at high hydrogen pressures in terms of the surface mechanisms. This field is now entering a scientific stage where a detailed theory of low-temperature, plasma-assisted growth can be developed.     

Reversible Vertical Manipulations of Single Pt Adatom on Pt（111） Surface with a Triple-Apex Tip

With a triple-apex tip, we investigate theoretically the vertical manipulation of single Pt adatom on the Pt（111） surface. The adatom adsorbed on the f cc site of the flat Pt（111） surface can be transferred vertically to the tip by adjusting the tip height properly. Moreover, based on the strong vertical trapping ability and the relatively weak lateral trapping ability of the tip, we propose a simple method to realize a reversible vertical manipulation of the Pt adatom from the highly coordinated sites, the kink and the step sites, of the stepped Pt（111） surface. All the vertical manipulations are completed using only the atomic force between the tip and the adatom, without the electric field.     

Laser-induced etching of silicon

Conventional fabrication method of porous silicon is anodisation of single crystal silicon in hydrofluoric acid. In this report, we show that it is possible to fabricate porous silicon by laser-induced etching. An earlier report by us has demonstrated the dependence of porous silicon photoluminescence characteristic on the etching laser wavelength [1]. Here we used 780 nm line from a diode laser as the etching source, and the optimum etching conditions were obtained. A simple model was proposed to explain the etching process. Scanning Electron Microscope (SEM) images of the samples support the proposed process.     

Reliable Lateral Manipulation of Single Adatom on Metal fcc（lll） Surfaces with a Single-Atom Tip

Using molecular statistics simulations based on the embedded atom method potential, we investigate the reliability of the lateral manipulation of single Pt adatom on Pt（111） surface with a single-atom tip for different tip heights （tip-surface distance） and tip orientations. In the higher tip-height range, tip orientation has little influence on the reliability of the manipulation, and there is an optimal manipulation reliability in this range. In the lower tip- height range the reliability is sensitive to the tip orientation, suggesting that we can obtain a better manipulation reliability with a proper tip orientation. These results can also be extended to the lateral manipulation of Pd adatom on P d （111） surface.     

Promotors,poisons and surfactants: Electronic effects of surface doping on metals

The interaction of adsorbates with metal surfaces is discussed. It is shown that the evanescent charge density produced by occupied sp derived surface states yields a considerable contribution to the Pauli repulsion experienced by adsorbate particles with a closed-shell electronic structure, e.g. rare-gases or molecules such as H₂ or N₂. For rare-gases this results in a reduction of the binding energy in the presence of occupied surface states, for molecules this gives rise to an additional contribution to the dissociation barrier. Suitable surface dopants are able to depopulate surface states and thereby to reduce the dissociation barrier. Such dopants can substantially promote catalytic reactions in which the dissociation from the gas phase or a physisorbed precursor is the rate limiting step. In contrast to closed-shell systems the bonding interaction for metal adsorbates on metal substrates is enhanced by occupied surface states. This leads to an extra diffusion barrier at steps, because the surface state amplitude drops to zero at upper step edges. The additional step-edge barrier, which is a kinetic hindrance for layer-by-layer growth, can be reduced by surface dopants depopulating the corresponding surface state. Such dopants promote layer-by-layer growth and act therefore as surfactants. It is concluded that the effect of promoters in catalysis and of surfactants in metal epitaxy is in part due to the same basic mechanism, namely the depopulation of surface states.     

Theoretical study of Ti and Fe surface alloys on Al(0 0 1) substrate

Accurate density-functional calculations are performed to investigate the formation of Ti and Fe ultrathin alloys on Al(0 0 1) surface. It is demonstrated that a deposition of Ti monolayer on Al(0 0 1) substrate leads to the formation of Al₃Ti surface alloy with Ti atoms arranged according to the L1₂ stacking, distinct from the D0₂₂ structure characteristic of a bulk Al₃Ti compound. A quest for the reason of this distinct atomic arrangement led us to the study of the surface structure of Al₃Ti(0 0 1) compound. It is concluded that even the Al₃Ti(0 0 1) surface is terminated with three layers assuming a L1₂ stacking and hence this stacking fault can be classified as a surface-induced stacking fault. Several possibilities of Fe atoms distributed in the surface region of Al(0 0 1) have been examined. The most stable configuration is the one with the compact Fe monolayer on Al(0 0 1) and covered by one Al monolayer. Lastly, our calculations show that there is no barrier for the penetration of Fe adatoms below the Al(0 0 1) surface; however, such a barrier is present for a Ti-alloyed Al(0 0 1) surface.     

Laser photochemical etching of silicon

Argon laser induced chemical etching of single crystal silicon with chlorine is studied. Etch rates are determined as a function of gas pressure, crystal orientation, laser power and wavelength. Analysis of gas phase and surface products by Fourier transform IR and X-ray photoelectron spectroscopy are used to probe the reaction mechanism. Contrary to previous reports, no thermally enhanced etch rate is observed for Si (111) and the presence of oxide on the surface is found to inhibit etching even at high laser power.     

Dopant-enhanced ablation of nitrocellulose by a nitrogen laser

The photoetching behavior of pure nitrocellulose and of nitrocellulose dyed with stilbene-420, coumarin-120 and rhodamine 6G by 337 nm nitrogen laser pulses has been studied. Ablation with a low power nitrogen laser is hereby reported for the first time. A two step photochemical mechanism is proposed to account for the ablation of the pure material. With the addition of dyes strongly absorbing at 337 nm the photoetching rate of nitrocellulose can be increased significantly. This increase is proportional to the molar extinction coefficient of the dye at 337 nm and its concentration in the polymer. The photoetching mechanism and the energy transfer processes from the dye to the polymer are discussed in detail.     

Photoluminescence of Anisotropically etched silicon

Visible room-temperature luminescence of Anisotropically Chemically Etched (ACE) silicon under spontaneous chemical surface modification in HNO₃:HF solution is reported. The material is investigated by SEM, AES, IR transmission and Raman scattering methods.     

Laser-induced chemical etching of silicon in chlorine atmosphere

Laser-induced chemical etching of single-crystalline (100) Si in Cl₂ atmosphere has been investigated for continuous Ar⁺ and Kr⁺ laser irradiation at around 351 nm, and at 457.9, 488.0, 514.5, and 647.1 nm. For laser irradiances below 10⁵ W/cm² the etching mechanism is non-thermal, and is based on photo-generated electron-hole pairs within the Si surface and Cl atoms produced within the gas phase. The experimental results are compared with model calculations.     

Steps,facets and nanostructures: investigations of Cu (11n) surfaces

Step structure and dynamics and adsorbate-induced reconstruction of stepped surfaces are useful features for investigating fundamental surface phenomena and their practical consequences. In this respect, vicinal Cu (11n) surfaces with n=3, 5 and 9 were studied by scanning tunneling microscopy (STM) at 300 K. While the regular monoatomic steps fluctuate for Cu (119), they are apparently stabilized for n≤5 by their strong repulsive interaction and this leads to a very low kink activity. In addition to the regular steps, the formation of double steps was observed as a particular phenomenon on those surfaces. These double steps determine the dynamic behavior at room temperature. By applying existing models for the fluctuations of the step positions in space and time, the formation energy for kinks at these double steps was determined to be 0.16 eV for Cu (115). According to this evaluation, diffusion along step edges is the dominating mass-transport mechanism. A model for the structure of the double steps and for the atomic displacement processes necessary for kink migration at these steps is presented. Complete faceting is observed for these surfaces upon oxygen adsorption at elevated temperatures (around 500 K) and was studied in detail for n=5 and 9. Both surfaces reconstruct into two types of {104} facets and a third facet, the orientation of which is determined by the macroscopic crystal orientation. The facet size is governed by the formation kinetics and can be controlled by varying the crystal temperature or the oxygen partial pressure. The formation kinetics is discussed as a nucleation and growth process and the relevant parameters are given. Facets within a range of size between 5 nm and 100 nm could thus be produced. They remained stable at ambient atmosphere, up to about 620 K, and also if covered by additional metal layers such as Ni. Received: 1 June 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Rapid thermal annealing of electrically-active defects in virgin and implanted silicon

Chemical etching of single-crystalline (100)Si induced by pulsed laser irradiation at 308, 423, and 583 nm has been investigated as a function of the laser fluence and C1₂ pressure. Without laser-induced surface melting, etching requires Cl radicals which are produced only at laser wavelengths below 500 nm. With low laser fluences ((308 nm)<100 mJ/cm²) etching is non-thermal and based on direct interactions between photocarriers and Cl radicals. For fluences which induce surface melting ((308 nm)>440 mJ/cm²) etching is thermally activated. In the intermediate region both thermal and non-thermal mechanisms contribute to the etch rate.     

Low temperature fabrication of 5-10 nm SiO2/Si structure using advanced nitric acid oxidation of silicon (NAOS) method

We have developed the advanced nitric acid oxidation of Si (NAOS) method to form relatively thick (5-10 nm) SiO₂/Si structure with good electrical characteristics. This method simply involves immersion of Si in 68 wt% nitric acid aqueous solutions at 120 °C with polysilazane films. Fourier transform infrared absorption (FT-IR) measurements show that the atomic density of the NAOS SiO₂ layer is considerably high even without post-oxidation anneal (POA), i.e., 2.28 × 10²² atoms/cm², and it increases by POA at 400 °C in wet-oxygen (2.32 × 10²² atoms/cm²) or dry-oxygen (2.30 × 10²² atoms/cm²). The leakage current density is considerably low (e.g., 10⁻⁵ A/cm² at 8 MV/cm) and it is greatly decreased (10⁻⁸ A/cm² at 8 MV/cm) by POA at 400 °C in wet-oxygen. POA in wet-oxygen increases the atomic density of the SiO₂ layer, and decreases the density of oxide fixed positive charges.     

Mismatch dislocations caused by preferential sputtering of a platinum-nickel alloy surface

Preferential sputtering and recoil mixing of a Pt₂₅Ni₇₅(111) single crystal surface leads to platinum enrichment in the upper monolayers, thereby increasing the lattice constant in these layers. This results in subsurface lattice mismatch dislocations, which have been studied by scanning tunneling microscopy. While the subsurface dislocations are only visible as shallow ditches in STM topographs, the Burgers vectors of the dislocation system can be determined by means of atomically resolved images of dislocations reaching the surface. A comparison with simulations of lattice relaxation using embedded-atom potentials shows good agreement with STM data and further allows the determination of the thickness of the Pt enrichment. We have estimated the Pt concentration in these layers from the dislocation density and studied the annealing behaviour of the surface.     

Surface dynamics and breakdown patterns of a random solid subject to a biased 3D etching

We propose a selective disaggregation model in three dimensions with a mixed Brownian-deterministic motion of the etchant particle driven by a tuning parameter taking into account the presence of an external field. The width of the surface sites in saturation is described by the Edwards-Wilkinson scaling law as in a ballistic selective decay process. Besides, we consider the surfaces resulting when the solid substrate is completely eroded up to the electrical breakdown. In this situation, we analyse the effects of the etchant particle motion on the topology and conductivity of the residual substrate and we compare the relevant patterns with the ones related to the classical percolation theory. These results may interpret some recent experimental findings in electrochemical nanotechnology.     

Plasma and surface modeling of the deposition of hydrogenated carbon films from low-pressure methane plasmas

The elementary mechanisms are described which determine the plasma and surface processes during the plasma-enhanced chemical vapour deposition of hydrogenated carbon films from methane. Corresponding model calculations are reviewed and critically discussed in comparison to experimental results. A realistic modeling requires the simultaneous and self-consistent treatment of plasma and surface effects. Several experimental data sets on plasma parameters and the growth and the composition of the films have been reproduced successfully. However, a broader experimental data base is needed for more critical tests of the models. The reliability of the modeling, in particular of the surface effects, is still limited due to the poor availability of elementary data.     

The formation of subsurface oxygen on Pt(100)

PhotoEmission Electron Microscopy (PEEM) enables imaging a surface via its work function. If a CO covered Pt(100) surface is exposed to oxygen patches are formed which appear dark in the PEEM image due to their high work function. As the surface is heated to temperatures above 650 K we observe the conversion of these dark islands into very bright ones with work functions much lower than even that of the clean surface. These findings are attributed to a change in the dipole moment of the adsorbed oxygen induced by their migration beneath the surface. A total work-function decrease of up to 1.2 eV has been evaluated independently using a Scanning Photoemission Microscope (SPM). The properties of this new kind of oxygen were also further investigated with thermal desorption spectroscopy and with Auger-electron spectroscopy.     

Kinetics of domain wall pinning in an incommensurate Pb overlayer on a Cu(110) surface

We have used grazing incidence X-ray scattering to study the kinetics of domain wall pinning during the transition between an incommensurate phase and a domain wall glass phase. The growth of both domain wall density and domain size are described by power-laws. The results are discussed in the context of recent theoretical models of growth.