Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

Influence of interfactants on thin metal film growth

The growth of Pb on Si(1 1 1) with and without Ag as an interfactant is studied in the temperature range from 270 to 375 K by microscopy and spectroscopy. Whereas Pb grows on the Si(1 1 1)-7×7 surface in the Stranski–Krastanov (SK) mode, the growth mode on the Si(1 1 1)-√3×√3-R30°-Ag surface changes from layer-by-layer below 300 K to SK mode above 300 K. Spectroscopy shows that Ag remains at the interface between the substrate and the growing Pb film. The influence of the interfactant on the growth is attributed to the increase of the island density by an order of magnitude and to the changes of the growth kinetics resulting from this increase.     

Oxidation of heated diamond C(100):H surfaces

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O^*₂). In this paper, the oxidation is performed at substrate temperatures from T_sub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED).

The oxygen coverage (θ) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage (θ) was lower at higher temperatures. For example, θ plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to T_sub=600°C, lost 60% of their adsorbed oxygen. ELS revealed few C=C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C–H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.     

Initial growth process and surface structure of Ag on Si(111) studied by low-energy Ion-Scattering Spectroscopy (ISS) and LEED-AES

The growth process of silver on a Si(111) substrate has been studied in detail by low-energy ion-scattering spectroscopy (ISS) combined with LEED-AES. Neon ions of 500 eV were used as probe ions of ISS. The ISS experiments have revealed that the growth at room temperature and at high temperature are quite different from each other even in the submonolayer coverage range. The following growth models have been proposed for the respective temperatures. At room temperature, the deposited Ag forms a two-dimensional (2D) island at around 2/3 monolayer (ML) coverage, where the Ag atoms are packed commensurately with the Si(111)1 substrate. One third of the substrate Si surface remains uncovered there. Then it starts to develop into Ag crystal, and at a few ML coverage a 3D island of bulk Ag crystal grows directly on the substrate. An intermediate layer, which covers uniformly the whole surface before the growth of Ag crystal, does not exist. At high temperatures (>~200°C), the well-known Si(111)√3-Ag layer is formed as an intermediate layer, which consists of 2/3 ML of Ag atoms and covers the whole surface uniformly. These Ag atoms are embedded in the first double layer of the Si substrate. It is concluded that the formation of the √3 structure needs relatively high activation energy which may originate from the large displacement of Si atoms owing to the embedment of the Ag atoms, and does not proceed below about 200°C. The most stable state of the Ag atoms on the outermost Si layer is in the shape of an island, both for the Si(111) surface and for the Si(111)√3-Ag surface.     

Growth and ordering of Ni(II) diphenylporphyrin monolayers on Ag(111) and Ag/Si(111) studied by STM and LEED

The room temperature self-assembly and ordering of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) on the Ag(111) and Ag/Si(111)-(√3 × √3)R30° surfaces have been investigated using scanning tunnelling microscopy and low-energy electron diffraction. The self-assembled structures and lattice parameters of the NiDPP monolayer are shown to be extremely dependent on the reactivity of the substrate, and probable molecular binding sites are proposed. The NiDPP overlayer on Ag(111) grows from the substrate step edges, which results in a single-domain structure. This close-packed structure has an oblique unit cell and consists of molecular rows. The molecules in adjacent rows are rotated by approximately 17° with respect to each other. In turn, the NiDPP molecules form three equivalent domains on the Ag/Si(111)-(√3 × √3)R30° surface, which follow the three-fold symmetry of the substrate. The molecules adopt one of three equivalent orientations on the surface, acting as nucleation sites for these domains, due to the stronger molecule-substrate interaction compared to the case of the Ag(111). The results are explained in terms of the substrate reactivity and the lattice mismatch between the substrate and the molecular overlayer.     

Chlorine/silicon surface reactions under heating

Reactions on Cl-adsorbed Si(111) and Si(100) surfaces—(Cl/Si(111) and Cl/Si(100))—under heating in ultrahigh vacuum (UHV) and in a Cl₂ atmosphere were studied. Auger electron spectroscopy (AES) and low-energy electron energy loss spectroscopy (LEELS) were used for examination of surface changes. Heating in UHV at 820°C for 30 s successfully removed almost all Cl atoms, both on Cl/Si(111) and Cl/Si(100). Variance in LEELS spectra shows that decomposition of SiCl_x (x > 1), a small amount of which was present on Cl/Si(111), occurs under heating on Si(111) both in UHV and in Cl₂ and desorbs reaction products, leaving the Si---Cl bonds on the surfaces. Such Si---Cl bonds specific to those on Cl/Si(111) are formed also on Cl/Si(100) heated in C1₂ at 820°C. On Cl/Si(100) heated in C1₂, there are various surface changes: relaxation of the 2 × 1 structure remaining on the Cl/Si(100), desorption of reaction products, and formation of Si---Cl bonds specific to those on Cl/Si(111). The Si---Cl bonds, both on Cl/Si(111) and Cl/Si(100), decomposed under longer heating and under heating at higher temperatures in UHV.     

Surface mass transport of Ag and In on vicinal Si(111)

Mass transport of Ag and In on vicinal Si(111) has been investigated by scanning Auger microscopy (SAM). Highly anisotropic surface diffusion and surface electromigration due to direct current were observed for Ag and In adatoms on 0°−, 0.5°−, 3°− and 6°−off vicinal Si(111) surfaces. The diffusion on the intermediate layer is strongly enhanced in the direction parallel to the step edge for Ag adatoms, while it is remarkably suppressed in the direction perpendicular to the step edge for In adatoms. The activation energy of the diffusion for the Ag adatoms ranged between 0.81 and 1.3 eV, while that for In adatoms increased from 0.31 to 0.66 eV with increasing the vicinal angle. The anisotropic diffusion transport is explained in terms of the step structure and the difference in the binding energy at the step site and the terrace site.     

Surface reconstructions of the Si(100)–Ge system

The surface reconstruction of epitaxial Ge layer on Si(100) was studied with ultrahigh vacuum scanning tunneling microscopy. The surface with 0.8 ML Ge grown in the presence of a hydrogen surfactant reveals the same structures as found in chemical-vapor-deposited Ge on Si(100): (i) defective (2×1) structure at 290°C, (ii) irregular (2×N) in Ge layer and defective (2×1) in bare Si regions at 420°C, and (iii) (2×N) in Ge-covered regions and c(4×4) in bare Si regions at 570°C. The morphology of step edges does not change with temperature, implying that the c(4×4) reconstruction is anisotropic in nature.     

Scattering of N2 from Ni(111)

A cold (T_rot<10 K) beam of N₂ with an initial translational energy of 0.40 eV strikes an Ni(111) surface at surface temperatures from 300 to 873 K at several incident angles from 15 to 60°. The rotational energy and angular distributions of the scattered molecules are probed using (2+1) resonance-enhanced multiphoton ionization. Molecules scattered in the specular direction have mean rotational energies that are independent of surface temperature, whereas those scattered at angles far from the specular show a dependence on surface temperature, caused likely by multiple collisions with the surface before escape. A rotational rainbow, seen in systems such as CO–Ni(111) and N₂–Ag(111), is not seen in this system. For molecules that scatter close to the specular direction, approximately 10% of the initial translational energy is converted into rotational energy of the scattered N₂. For surface temperatures above room temperature, the angular distributions indicate that molecules that scatter into low-J states also tend to exit in a broad peak (10–20° FWHM) near the specular, and this peak is broadened with increasing incident angle. The molecules that scatter into high-J states have a much broader distribution, indicating that they are trapped rotationally during the initial collision and suffer multiple collisions before leaving the surface.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

An investigation of the Si(111)−(√3 × √3)R30°−Ag surface by Li impact collision ion scattering spectroscopy

The Si(111)−(√3 × √3)R30°−Ag surface has been investigated using the technique of Li⁺ impact collision ion scattering spectroscopy. Typical LEED √3 domain sizes were estimated to be on the order of 150 Å for a 1 ML coverage of Ag, with the √3 structure persisting for coverages of Ag up to 35 ML. Silver islanding was found to influence the appearance of the 5 keV Li⁺ ICISS angular scans even for 1 ML coverages of Ag deposited at 480°C. A detailed structural analysis of the Si(111)−√3−Ag surface (0.25 ML deposition) involved the comparison of 5 keV Li⁺ ICISS experimental data along the [11 ], [ 10] and [2 1] azimuths with computer simulations of the scattered ion intensities based on previously proposed models for the √3 surface. Nine structurally different models were tested, and only the missing-top-layer (MTL) and the honeycomb-chained-trimer (HCT) models were found to be consistent with all the experimental results. An estimate of 0.4 Å for the maximum downward vertical displacement of the Ag atoms with resect to the surface Si atoms in the MTL model is made. The effects of increased thermal vibrational amplitude in the simulation of Si---Ag shadowing effects is also discussed. The interpretations of previous noble gas ICISS results are shown to be inconsistent with the present alkali metal ICISS study of the √3 surface.     

The Ti/c-Si solid state reaction III. The low-temperature reaction kinetics

Thin Ti layers (≈10nm) are grown on top of a clean Si(111) substrate. Heating these layers initiates a solid state reaction, yielding a monosilicide phase at ≈350°C and a C49 disilicide at ≈450°C. The present study concerns the growth kinetics of both phases by means of ellipsometry. A diffusion-limited growth kinetics is found for the monosilicide formation. However, two growth rates are observed, a fast initial one and a slow terminal growth rate. An enhanced Si diffusion in atomically disordered regions as compared to well ordered regions (grains or clusters) could be an explanation. From the measurements we have found a value of 2×10^-15 cm²/s for the diffusion coefficient at ≈370°C and an activation energy of 0.62 ± 0.1 eV. Both values correspond to the fast process. Subsequently increasing the temperature to ≈450°C permits the growth of the homogeneous C49 TiSi₂ phase. For this process, both planar layer growth and intermixing are observed, however, quantitative results could not be derived from the present study.     

Changes of phase and intensity of optical SHG with Ag deposition on Si(111)-7×7 surfaces

The phase and intensity of optical second harmonic generation (SHG) were studied in Ag deposition on the Si(1 1 1) surfaces. The 7×7 reconstruction of the surface changed to the 1×1 structure in room temperature deposition. The SHG intensity reduced and the phase shifted to +180° with this structural change. Meanwhile, the 7×7 reconstruction changed to the reconstruction in 400 °C deposition. With this structural change, the SHG intensity increased and the phase shifted to −250°. An analysis with anharmonic oscillator model showed that the changes in room temperature deposition were due to the quenching of the surface dangling bond states of the 7×7 reconstruction by the Ag deposition, whereas those in 400 °C deposition were due to the appearance of new surface states of the reconstruction.     

The Ti/c-Si solid state reaction I. An ellipsometrical study

This paper is the first of a series of three articles in which we present the results and analyses of an extended study of the c-Si/Ti solid state reaction. In this paper we will discuss the spectroscopic ellipsometric investigation. Thin (≈10nm) Ti films are grown on clean Si(111) surfaces and are subsequently heated. The Si indiffusion and the Si-Ti intermixing are continuously registered by three-wavelengths ellipsometry. Two metastable intermediate phases are observed to form before the final state is obtained Spectroscopic ellipsometry (E = 2−4.5 eV) is used to characterize the as-deposited layer, the metastable intermediate phase and the final state. Analysis of these spectra shows that: (1) Si and Ti intermix during the initial Ti deposition, (2) a fast reordering of the Ti atoms occurs when the system is slightly heated (≈175°C), (3) a metastable, probably monosilicide phase with a large Si concentration gradient is obtained at ≈350°C, (4) a homogeneous metastable TiSi₂ forms at ≈450°C, at ≈700°C a roughened TiSi₂ layer with a surplus of c-Si is formed.     

Initial stages of praseodymium growth on Si(111): morphology and electronic structure

An STM study of the Pr---Si(111)-(7 × 7) interface reveals a much more heterogeneous growth morphology than is suggested by diffraction techniques and spectroscopies which average over the surface. Deposition of 1 ML followed by annealing at 650°C gives the most orderly growth, but this falls short of 2D epitaxy. At high temperatures (> 1000°C), the small amount of rare earth remaining on the surface stabilises some novel Si(111) surface reconstructions.     

Electronic properties and atomic arrangement of the Ag/Si(111) interface

Variations of the work function and photoelectric yield spectra of a Ag/Si(111) system were investigated as a function of Ag film thickness and substrate temperatures. It was clarified that monolayer deposition of Ag onto Si at room temperature cause a decrease in the work function, while the deposition at 500°C did an increase. The results could be closely correlated with the atomic arrangement derived from low-energy ion scattering spectroscopy and low-energy electron diffraction.     

New surface structure analysis of Ag-Si phase by quantitative auger electron spectroscopy method

Ag or Au was deposited on a clean Si substrate at room temperature. These systems, Ag/Si and Au/Si, were annealed at various temperatures or various heating times. Due to the annealing, Ag or Au diffused into Si and/or Si diffused into the metal. The changes of the surface composition are analyzed by a quantitative Auger Electron Spectroscopy (AES) method which is newly developed as a non-destructive method. In the case of Ag/Si, Ag migrated into the Si substrate and/or Si diffused into Ag. Then, Ag-Si solid solution was produced. After the annealing, the Ag/Si system is changed into Ag/(Ag-Si)/Si of the three-phase structure. In the case of Au/Si (Au film thickness < 15 Å), the Au film thickness became thinner by annealing. The Au/Si system always keeps the Au/Si phase after annealing, while there was no Au-Si solution area. The difference between the Ag/(Ag-Si)/Si and the Au/Si structure is attributed to the reason that Au diffuses more quickly than Ag into the Si substrate. AES results after annealing cannot be explained by the model of the formation of the three-dimensional island structure which is commonly referenced.     

Ellipsometric spectroscopy study of photoluminescent Si/SiO2 systems obtained by magnetron co-sputtering

Si nanograins embedded in silica matrix were obtained by magnetron cosputtering of both Si and SiO₂ at different substrate temperature (200–700°C) and thermal annealing at 1100°C. The samples were characterized by ellipsometric spectroscopy, high-resolution electron microscopy observations and photoluminescence. The highest excess of Si atoms was found to be incorporated for deposition temperature near 400–500°C, giving rise to a maximum PL and a shift of the peak position towards lower energy. These features might be interpreted in terms of quantum size effects and of density of grains, even though the interface states seem to be involved in the improvement of the photoluminescence efficiency.     

Alignment of Ge nanoislands on Si(111) by Ga-induced substrate self-patterning

A novel mechanism is described which enables the selective formation of three-dimensional Ge islands. Submonolayer adsorption of Ga on Si(111) at high temperature leads to a self-organized two-dimensional pattern formation by separation of the 7 x 7 substrate and Ga/Si(111)-(square root[3] x square root[3])-R30 degrees domains. The latter evolve at step edges and domain boundaries of the initial substrate reconstruction. Subsequent Ge deposition results in the growth of 3D islands which are aligned at the boundaries between bare and Ga-covered domains. This result is explained in terms of preferential nucleation conditions due to a modulation of the surface chemical potential.     

The effects of a trace addition of silver upon elevated temperature ageing of an Al–Zn–Mg alloy

Microalloying additions of Ag (0.1 at.%) increase the hardening response of Al–Zn–Mg alloys to elevated temperature ageing in the range 100–200°C due to the formation of a high density of very fine η′ precipitate plates. The present study employed transmission electron microscopy (TEM) and three-dimension atom probe (3DAP) to study the early stages of ageing in the alloy Al–1.8Zn–3.4Mg–0.1Ag (at.%) in an attempt to identify the role of Ag in stimulating precipitation hardening. During isothermal ageing at 90°C, the hardening response is attributed to a high density of Zn–Mg–Ag rich solute clusters and GP zones. During ageing at 150°C, η′ precipitates nucleate at Zn–Mg–Ag rich solute clusters, the former growing as {111} platelets with an average composition of approximately 20 at.% Zn, 20 at.% Mg and 1.4 at.% Ag. The 3DAP data indicates that the co-segregation of Zn and Ag and subsequently Zn and Mg atoms precedes the formation of the Zn–Mg–Ag rich solute clusters. The GP zones and η′ precipitates were observed to possess a Zn:Mg ratio close to 1:1, whereas the equilibrium η precipitates possessed compositions consistent with MgZn₂. Furthermore, partitioning of Ag was observed inside all precipitate phases, viz. G.P. zones, η′ and η.