Dissociative adsorption and site specificity in the initial stages of tetraethoxysilane (TEOS) interaction with Si(111)-(7×7)

We report results of a scanning tunneling microscopy and X-ray photoelectron spectroscopy study on the interaction of tetraethoxysilane (TEOS), a precursor for chemical vapor deposition of silicon dioxide, with Si(111)-(7×7) at room temperature. Under these conditions the interaction of TEOS with the surface is predominantly dissociative. The main adsorption products are ethyl- and triethoxysiloxane groups, which probably evolve in a four-center reaction of TEOS with two neighboring surface dangling bonds. Adsorption of the dissociation products is highly site-selective: triethoxysiloxane groups adsorb on the Si adatoms while ethyl groups react with the rest-atom dangling bonds. Center adatoms are over three times more reactive towards this reaction than corner adatoms. This two-fold selectivity is explained within the concept of local electron donor/acceptor properties.     

Sodium adsorption on a Ge(100)-(2 × 1) surface

The adsorption of Na on a Ge(100)-(2 × 1) surface has been studied by means of AES, LEED, EELS, TPD and work-function measurements. In the submonolayer coverage region the coverage dependencies of the desorption activation energy E(Θ) and desorption frequency v(Θ) have been determined using the threshold TPD method. Our experimental data show that after the completion of the first Na layer, 3D crystallites develop on the Na/Ge(100) surface (Stranski-Krastanov growth mode). For Θ > 1 ML, formation, followed by decomposition of a certain Na---Ge surface compound occurs in the temperature range 410–550 K.     

Adsorption and thermal decomposition of diethylaluminum hydride on Si(1 0 0)-2 × 1

Chemistry of organoaluminum compounds on silicon surfaces forms a foundation of chemical vapor deposition (CVD) for the formation of metal-semiconductor interconnects. We have applied multiple internal reflection Fourier-transform infrared spectroscopy and thermal desorption mass spectrometry to analyze the chemistry of one of the promising Al-CVD precursors, diethylaluminum hydride, on a Si(1 0 0)-2 × 1 surface. Diethylaluminum hydride adsorbs molecularly on this surface both at room temperature and at 100 K. Thermally induced surface reaction consumes the monolayer of adsorbed organoaluminum molecule. The only hydrocarbon product is ethylene desorbing from the silicon surface around 600 K. Despite a clean reaction that removes carbon from the surface, aluminum deposition is not significant because of the formation of alane products.     

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.     

A comparative infrared study of H2O reactivity on Si(1 0 0)-(2 × 1), (2 × 1)-H, (1 × 1)-H and (3 × 1)-H surfaces

The water adsorption on the bare and H-terminated Si(1 0 0) surfaces has been studied by the BML-IRRAS technique. It is found that H-terminated surfaces are much less reactive compared to the bare silicon surfaces. The (1 × 1)-H and (3 × 1)-H surfaces show similar and less reactivity pattern compared to the (2 × 1)-H surface. At higher exposures, the water reaction with coupled monohydride species provides an effective channel for oxygen insertion into the back bonds of dihydride species. It is not attributed to the H–Si–Si–H + H₂O → H–S–Si–OH + H₂, which could give rise to the characteristic Si–H and Si–OH modes, respectively at 2081 and 921 cm⁻¹. A more suitable reaction mechanism involving a metastable species, H–Si–Si–H + H₂O → H₂Si  HO–Si–H (metastable) explains well the bending modes of oxygen inserted silicon dihydride species which are observed relatively strongly in the reaction of water with H-terminated Si(1 0 0) surfaces.     

Structure of the Si(011)-(16 × 2) surface and hydrogen desorption kinetics investigated using temperature-programmed desorption

D₂ temperature-programmed desorption (TPD) was used to probe the structure of the Si(011)-(16 × 2) surface. Deuterium was adsorbed at 200°C to coverages θ_D ranging up to complete saturation (approximately 1.1 ML) and the sample heated at 5°C s⁻¹. TPD spectra exhibited three second-order desorption peaks labelled β₂, β*₁ and β₁ centered at 430, 520 and 550°C. Of the proposed models for the Si(011)-(16 × 2) reconstruction, the present TPD results as a function of θ_D provide support for the adatom/dimer model with the β₂ peak assigned to D₂ desorption from the dihydride phase, while the β*₁ and β₁ peaks arise from adatom and surface-atom monohydride phases.     

STM study of low pressure adsorption of silane on Si(111)7 × 7

We report a study of silane adsorption on the Si(111)7 × 7 surface. We have been interested in the first stages of chemisorption at room temperature. Reactive sites of the unit cell have been clearly identified on Scanning Tunneling Microscopy (STM) images: the reaction involves the rest atom and the adjacent adatom of the DAS structure with preferential adsorption on the center adatom. We propose an original chemisorption mechanism which leads to the formation of two SiH₂ species by chemisorption and involves the breaking of Si---Si backbonds of the adatom.     

Core level photoemission and STM characterization of Ta/Si(1 1 1)-7 × 7 interfaces

We present the results of scanning tunneling microscopy (STM) and photoemission spectroscopy (PES) of the Ta/Si(1 1 1)-7 × 7 system after deposition of Ta at substrate temperatures from 300 to 1250 K. The coverage of Ta varied from 0.05 up to 2.5 of a monolayer (ML). STM shows that at 300 K and coverage less than 1 ML, a disordered chemisorbed phase is formed. Deposition on a hot surface (above 500 K) produces round 3D clusters randomly distributed on the surface. Cluster height and their diameter are found to change drastically with annealing temperature and the Ta coverage. Analysis of photoemission data of the Si 2p core levels shows that at room temperature and at coverage ?1 ML core level binding energy shifts and intensity variations of Si surface related components are observed, which clearly indicate that the reaction starts already at 300 K. Shifts in the binding energy, changes of the peak shapes and intensity of the Ta 4f doublet at higher temperatures can be explained by the formation of stable silicide on the surface.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

Formate stability and carbonate hydrogenation on strained Cu overlayers on Pt(1 1 1)

Formate (HCOO) synthesis, decomposition and the hydrogenation of carbonate (CO₃) on Cu overlayers deposited on a Pt(1 1 1) single crystal are investigated to examine the reactivity of a Cu surface under tensile strain with defects present.Formate is synthesized from a 0.5 bar mixture of 70% CO₂ and 30% H₂ at varying temperatures, and the evolution is followed with polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). Subsequent TPD reveals decomposition of the formate species into CO₂ and H₂ at 420 ± 5 K for strained Cu at sub-monolayer to monolayer coverages. This is a significantly lower decomposition temperature than obtained earlier on pristine Cu(1 1 1) (460 K), as well as for thicker Cu layers where we assign an observed decomposition peak at 440 ± 5 K to relaxed, but defect-rich Cu(1 1 1). However, the thermal stability of formate on strained and defect-rich Cu is similar to previous results obtained for supported, and lattice-strained, Cu nanoparticles.The hydrogenation of carbonate produced by 0.3 bar CO₂ exposure at room temperature was monitored with XPS and TPD showing a significant loss of carbonate when subjected to 0.2 bar H₂ at room temperature. However, the presence of formate on the surface, or any other hydrogenation product, could not be established during or after H₂ exposure by PM-IRRAS, EELS or TPD. Even so, the results suggest that carbonate and its hydrogenation may constitute a relevant pathway to methanol production.     

Surface reactions and kinetically-driven patterning scheme for selective deposition of Si and Ge nanoparticle arrays on HfO2

We demonstrate a kinetically-driven patterning scheme to selectively position arrays of Ge or Si nanoparticles within lithographically defined HfO₂ windows. The surface reactions enabling patterning are revealed through temperature programmed desorption experiments and selectivity of the deposition is verified by X-ray photoelectron spectroscopy and scanning electron microscopy. Patterning is possible by exploiting the different reactivity of Ge and Si on HfO₂ and SiO₂ surfaces and employing a sacrificial SiO₂ mask on which adatoms etch the SiO₂ surface and do not accumulate to form nanocrystals.     

Transformations of C-type defects on Si(100)-2 × 1 surface at room temperature – STM/STS study

We present a scanning tunneling microscopy study of the C-type defects on the Si(100)-2 × 1 surface and their transformations into other defect forms at room temperature. A model of the C defect as a dissociated water molecule was adopted for interpretation of the observed transformations. We explained the transformations by hopping the H or OH between bonding sites on Si dimers. Newly, the most stable defect form, corresponding to the H and hydroxyl group adsorbed on the same dimer, is reported. Real time observations provided an explanation for the defect C2-C2 described earlier. A reversible transition of this defect into another form, not revealed yet, is presented. Electronic structure of the observed defects is studied by means of scanning tunneling spectroscopy. Measured spectra show semiconducting character of the C defect. Spectra of the other defect forms are discussed.     

Nucleation behaviour during silicon UHV-CVD on Si(111)7×7

We report a UHV-CVD homoepitaxy study on the Si(111)7×7 surface investigated with Scanning Tunnelling Microscopy (STM). We have investigated the two-dimensional island density in the temperature range from 450 to 550°C and silane pressure range from 2 to 8×10⁻⁴ Torr. Contrary to experiments using molecular beam epitaxy, we find that the two-dimensional island density in UHV-CVD cannot be directly described by the standard nucleation theory. We discuss this point and show that the variation of the steady-state hydrogen coverage on the surface during pressure- or temperature-dependent experiments can explain the observed two-dimensional island density behaviour.     

Surface chemistry of (2,4-dimethylpentadienyl)(ethylcyclopentadienyl)Ru on polycrystalline Ta

The adsorption and desorption of (2,4-dimethylpentadienyl)(ethylcyclopentadienyl)Ru [DER] on polycrystalline Ta have been studied by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). DER exposures to Ta at 140 K result in primarily molecular adsorption and desorption, while a minor surface reaction occurs at defect sites. Monolayer DER desorbs between 278 and 297 K with increasing coverage, exhibiting a first order, zero coverage desorption energy of 2.3 eV. Multilayer DER desorbs between 272 and 263 K, most likely with fractional order kinetics, and exhibits a zero coverage desorption energy of 0.9 eV. XPS Ru 3d binding energies increase with increasing coverage due to core hole screening in the monolayer regime and increasing sample charging as the DER overlayer becomes thicker in the multilayer regime. DER exhibits a three-dimensional (3D) “hit and stick” growth mode in which random 3D structures form due to the lack of adsorbate mobility at 140 K. DER exposures to Ta between 298 and 773 K result in minor decomposition resulting primarily in adsorbed hydrocarbon species on the surface. When the Ta is pre-covered with atomic iodine, DER dissociation is significantly decreased while adsorption is increased.     

Scanning tunneling microscopy and molecular orbital calculation of pentacene molecules adsorbed on the Si(100)2×1 surface

Adsorption of the organic molecule pentacene on Si(100)2×1 surfaces was imaged using scanning tunneling microscopy (STM). The molecular images exhibit distinct shapes corresponding to the expected shapes for adsorption configurations. Semi-empirical molecular orbital (MO) calculations reveal a local surface density of states for the adsorbed pentacene on the Si surface. In the cases where the pentacene molecule is adsorbed on an Si dimer row, the calculated MOs are in good agreement with the molecular images observed in STM. In the case of pentacene adsorbed on two or three Si-dimer rows, however, the MOs of the pentacene do not correlate directly with the observed STM images. It is thus considered that the STM images are produced by a combination of Si dimer states and MO.     

Surface state on the SiC(0001)-(√3 × √3) surface

An angle resolved photoemission study of a surface state on the SiC(0001)-(√3 × √3) surface is reported. Experiments carried out on the 6H and 4H polytypes give essentially identical results. A surface state band with semiconducting occupation is observed, centered around 1.0 eV above the valence band maximum (VBM) and with a width of about 0.2 eV. Recently calculated results for a Si-adatom-induced √3 × √3 reconstruction give a metallic surface state band centered about 1.2 eV above the VBM and with a width of 0.35 eV. The dispersion determined experimentally is smaller than calculated but exhibits the same trend, the surface state disperses downwards towards the VBM with increasing parallel wavevector component along both the qG--- and qG--- directions of the √3 × √3 surface Brillouin zone. The VBM is determined to be located at about 2.3(±0.2) eV below the Fermi level. The results indicate that Si adatoms on top of an outermost Si---C bilayer may be an inadequate structural model for explaining recent experimental findings for the SiC(0001)-(√3 × √3) surface.     

High resolution XPS studies on hexadecafluoro-copper-phthalocyanine deposited onto Si(1 1 1)7×7 surface

High resolution X-ray photoelectron spectroscopy measurements have been performed onto ultrathin films of hexadecafluoro copper phthalocyanine deposited, at room temperature and in ultrahigh vacuum conditions, onto clean Si(1 1 1)7×7 substrate (silicon, Si). The measurements, performed at various film thicknesses, show a strong interaction between the molecule and the Si substrate. All the core level peaks present strong modifications induced by the substrate interaction. In particular the fluorine (F) spectrum clearly presents the effect of the interaction of some F atoms of the molecule with the substrate, which determines the formation of F–Si bonds while the copper spectrum indicates a charge transfer from the Si substrate. The changes observed in the other core level spectra have been attributed to a different charge distribution in the molecule, after the formation of F–Si bonds. We suggest a planar growth of these molecules on the Si substrate starting from the first layer.     

First-principles study of adsorption and diffusion on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces

Using first-principles total-energy calculations, we have investigated the adsorption and diffusion of Si and Ge adatoms on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces. The dimer vacancy lines on Ge/Si(0 0 1)-(2 × 8) and the alternate S_A and rebonded S_B steps on Ge/Si(1 0 5)-(1 × 2) are found to strongly influence the adatom kinetics. On Ge/Si(0 0 1)-(2 × 8) surface, the fast diffusion path is found to be along the dimer vacancy line (DVL), reversing the diffusion anisotropy on Si(0 0 1). Also, there exists a repulsion between the adatom and the DVL, which is expected to increase the adatom density and hence island nucleation rate in between the DVLs. On Ge/Si(1 0 5)-(1 × 2) surface, the overall diffusion barrier of Si(Ge) along direction is relative fast with a barrier of ∼0.83(0.61) eV, despite of the large surface undulation. This indicates that the adatoms can rapidly diffuse up and down the (1 0 5)-faceted Ge hut island. The diffusion is also almost isotropic along [0 1 0] and directions.     

Mechanism of GeH4 dissociation on Si(1 1 1)-(7 × 7)

Results of an STM study of dissociative GeH₄ adsorption on Si(1 1 1)-(7 × 7) at 300 K show that GeH₄ adsorbs under scission of two Ge-H bonds according to GeH₄(g) + 4db → GeH₂(ad) + 2H(ad). GeH₂ binds to two adatom dangling bonds in a bridged configuration, while the two released hydrogen atoms saturate two additional dangling bonds. The GeH₄ sticking coefficient under these conditions is 1.2 × 10⁻⁶, one order of magnitude smaller than for SiH₄.     

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.