Photoemission study of CaF2 on Si(001)-2×1 during annealing

We have employed synchrotron radiation photoemission to investigate calcium fluoride deposited on Si(001)-2×1 annealed at 700 °C. The valence band spectra reveal that the initial molecules are dissociated to single Ca atoms resting on the surface. Si 2p core-level spectra manifest a negatively shifted Ca-induced line at 0.35 eV. The dissociated Ca atoms occupy only half of the surface, on top of which the CaF₂ molecules commence growth. This is in contrast to the Si(111)-7×7 counterpart, which exhibits a CaF layer in the interface. Strong elastic scattering due to the absorbed Ca atoms is evident in the photoemission spectra, thus averaging out the angle-dependent features.     

Transient-enhanced Si diffusion on natural-oxide-covered Si(0 0 1) nano-structures during vacuum annealing

The morphology of annealed patterned Si(0 0 1) wire templates was studied by several techniques. We found an enormous Si-mass transport on the Si surface at usual oxide desorption temperatures around 900°C under UHV conditions. Heat treatment of 5 min transforms the initially rectangular wire profiles with a height of 300 nm to flat (<100 nm) and faceted triangular ridges exhibiting thermodynamically preferred {1 1 1}- and {3 1 1}-facets.It was found that the natural SiO₂ on the predefined wire pattern must be responsible for the degradation of the wire structure. Removing the SiO₂ layer from the Si wires ex situ with an HF dip preserves the rectangular structures during high-temperature annealing. The Si–SiO₂ interface was investigated with high-resolution transmission electron microscopy to image the Si wire surface and the natural oxide layer in detail.     

Photoemission electron microscopy study of anthracene growth on Si(1 1 1)

The thin film growth of anthracene films on Si(1 1 1) surfaces is studied by photoemission electron microscopy (PEEM). The thin film growth of anthracene on Si(1 1 1) is similar to the growth of pentacene on silicon. Initially a layer of flat lying molecules chemisorbs on the surface. Subsequent growth of fractal islands with standing up molecules proceeds on top of this flat layer.     

Photoemission study of samarium on and CdTe(1 0 0)

Experimental photoemission results on and CdTe(1 0 0) surfaces on a function of samarium adsorbate coverage are presented. Energy distribution curves were recorded at photon energies around the Sm 4d→4f threshold (135–136 eV) to reveal the Sm contribution to the electronic structure and enhance the sensitivity. The evolution of core-level Ga 3d and Cd 4d spectra was also studied. The interaction of Sm with both GaN and CdTe leads to reactive interface formation. In the case of CdTe, it results in creation of an interfacial Sm–CdTe compound, which inhibits further diffusion of Sm into the bulk. The interaction of Sm with GaN leads to the release of Ga atoms on the surface and segregation of Ga clusters.     

The simulation study for the nanometer-scale selective growth of Si islands on Si(0 0 1) windows in ultrathin SiO2 films

The nanometer-scale selective growth of Si islands on Si(0 0 1) windows in ultrathin SiO₂ films are studied using the kinetic Monte Carlo simulation. The growth of Si islands is reproduced in simulation where we assume that the migration barrier energy for Si adatom on SiO₂ film is far lower than that on the Si surface at the window.     

Metal organic chemical vapor deposition of ultrathin ZrO2 films on Si(1 0 0) and Si(1 1 1) studied by electron spectroscopy

The growth of ultrathin ZrO₂ films on Si(1 0 0)-(2 × 1) and Si(1 1 1)-(7 × 7) has been studied with core level photoelectron spectroscopy and X-ray absorption spectroscopy. The films were deposited sequentially by chemical vapor deposition in ultra-high vacuum using zirconium tetra-tert-butoxide as precursor. Deposition of a > 50 Å thick film leads in both cases to tetragonal ZrO₂ (t-ZrO₂), whereas significant differences are found for thinner films. On Si(1 1 1)-(7 × 7) the local structure of t-ZrO₂ is not observed until a film thickness of 51 Å is reached. On Si(1 0 0)-(2 × 1) the local geometric structure of t-ZrO₂ is formed already at a film thickness of 11 Å. The higher tendency for the formation of t-ZrO₂ on Si(1 0 0) is discussed in terms of Zr-O valence electron matching to the number of dangling bonds per surface Si atom. The Zr-O hybridization within the ZrO₂ unit depends furthermore on the chemical composition of the surrounding. The precursor t-butoxy ligands undergo efficient C-O scission on Si(1 0 0), leaving carbonaceous fragments embedded in the interfacial layer. In contrast, after small deposits on Si(1 1 1) stable t-butoxy groups are found. These are consumed upon further deposition. Stable methyl and, possibly, also hydroxyl groups are found on both surfaces within a wide film thickness range.     

Photoemission study of cobalt interaction with the oxidized Si(1 0 0)2 × 1 surface

The interaction of cobalt atoms with an oxidized Si(1 0 0)2 × 1 surface was studied by photoelectron spectroscopy with synchrotron radiation at room and elevated temperatures. The SiO_x layer grown in situ on the crystal surface was ∼0.3 nm thick, and the amount of deposited cobalt was varied within eight atomic layers. It was found that Co atoms could penetrate under the SiO_x layer even at room temperature in the initial growth. As the Co amount increased, a ternary Co-O-Si phase was formed at the interface, followed by a Co-Si solid solution. Silicide synthesis associated with the decomposition of these phases started under the SiO_x layer at ∼250 °C, producing cobalt disilicide with a stable CaF₂-type of structure.     

Photoemission study of glycine adsorption on Cu/Au(1 1 1) interfaces

The adsorption of glycine on Au(1 1 1) pre-deposited with different amounts of Cu was investigated with both conventional X-ray photoelectron spectroscopy (XPS) and synchrotron-based photoemission. In the Cu submonolayer range, glycine physically adsorbs on the Cu/Au(1 1 1) surfaces in its zwitterionic form and completely desorbs at 350 K. The C 1s, O 1s and N 1s core level binding energies monotonically increase with Cu coverage. This indicates that, in the Cu submonolayer range, the admetal is alloyed with Au rather than forming overlayers on the Au(1 1 1) substrate, consistent with our recent experimental and theoretical results [X. Zhao, P. Liu, J. Hrbek, J.A. Rodriguez, M. Pérez, Surf. Sci. 592 (2005) 25]. Upon increasing the amount of deposited Cu over 1 ML, part of the glycine overlayer transforms from the zwitterionic form to the anionic form (NH₂CH₂COO⁻) and adsorbs chemically on the Cu/Au(1 1 1) surface with the N 1s binding energy shifted by −2.3 eV. When the amount of deposited Cu is at 3.0 or 6.0 ML, the intensity of the N 1s chemisorption peak increases with aging time at 300 K. It indicates that glycine adsorption induces Cu segregation from the subsurface region onto the top layer of the substrate. Judging from the initial N 1s peak intensities, it is concluded that 64% and 36% of the top layer are still occupied by Au atoms before glycine adsorption even when the amounts of deposited Cu are 3.0 and 6.0 ML, respectively. On the Au(1 1 1) surface pre-dosed with 6.0 ML of Cu, part of the chemisorbed glycine will desorb and part will decompose upon heating to 450-500 K. In addition, about 20% of the glycine exists in the neutral form when the glycine overlayer was dosed on Cu/Au(1 1 1) held at 100 K.     

In situ ESR observation of interface dangling bond formation processes during ultrathin SiO2 growth on Si(111)

We report the formation processes of interface dangling bonds (Pb centers) during initial oxidation of a clean Si(111) surface using an ultrahigh-vacuum electron-spin-resonance technique. At the oxidation of one or two Si layer(s), the Pb center density reached around 2.5-3.0 x 10(12) cm(-2), which is the same density as in the case of thick SiO2. This result shows that the Pb center density does not originate from the long-range accumulation of the structural stress between two materials, but from the chemical reactions of oxidation within a few Si atomic layers.     

Adsorption of molecular SiO2 on a clean Si(1 0 0) surface

We have investigated the adsorption of molecular (gaseous) SiO₂ on a clean Si(1 0 0) p(2 × 2) reconstructed surface using density functional theory based methods. The SiO₂ molecule is found to be chemisorbed on various sites on the Si surface and the most energetically favourable structure is on top of the dimers. The minimum energy pathways for the various adsorption channels indicate that the reaction is barrierless in all cases. The corresponding vibrational spectrum is also calculated and the adsorbed molecules are, as expected, found to have red-shifted vibrational frequencies. The energetically favourable adsorption sites and adsorption energies are comparable to the results found for SiO.     

Defect formation of Au thin films on SiO2/Si upon annealing

We have studied structural changes of Au film surfaces grown on Si with native oxide layers. Using X-ray photoelectron spectroscopy (XPS), we found that annealing above 200°C can cause formation of defects (or cracks), which is most likely driven by interdiffusion of Au and Si accompanying strong Au–Si interactions at the interface regime. Scanning tunneling microscopy (STM) study is also in line with defect formation upon annealing. Interaction of O₂ with rough Au surfaces is discussed in connection with catalytic activities of Au surfaces.     

SiO adsorption on a p(2 × 2) reconstructed Si(1 0 0) surface

We have investigated the adsorption mechanism of SiO molecule incident on a clean Si(1 0 0) p(2 × 2) reconstructed surface using density functional theory based methods. Stable adsorption geometries of SiO on Si surface, as well as their corresponding activation and adsorption energies are identified. We found that the SiO molecule is adsorbed on the Si(1 0 0) surface with almost no activation energy. An adsorption configuration where the SiO binds on the channel separating the dimer rows, forming a Si-O-Si bridge on the surface, is the energetically most favourable geometry found. A substantial red-shift in the calculated vibrational frequencies of the adsorbed SiO molecule in the bridging configurations is observed. Comparison of adsorption energies shows that SiO adsorption on a Si(1 0 0) surface is energetically less favourable than the comparable O₂ adsorption. However, the role of SiO in the growth of silicon sub-oxides during reactive magnetron plasma deposition is expected to be significant due to the relatively large amount of SiO molecules incident on the deposition surface and its considerable sticking probability. The stable adsorption geometries found here exhibit structural properties similar to the Si/SiO₂ interface and may be used for studying SiO_x growth.     

Ge dots on Si (1 1 1) and (1 0 0) surfaces with SiO2 coverage: Raman study

Germanium quantum dots formed on Si (1 1 1) and (1 0 0)-oriented surfaces coated with ultra-thin oxide layers are studied using Raman spectroscopy technique. Some structural properties (height, stoichiometry and mechanical stresses) of the dots were estimated from Raman data. For analysis of the experimental data, the Raman spectra of Ge nanoclusters containing some hundreds of Ge atoms were calculated numerically. The effects of the resonance enhancement of the intensity of Raman scattering in the Ge-nanoclusters–SiO₂–Si system were discussed. The influence of the lateral sizes of Ge nano-clusters on the frequencies of phonons localized in them was studied using numerical simulation. The influence of multi-layer growth on the structure of the Ge quantum dots was investigated.     

Specular X-ray reflectivity study of interfacial SiO2 layer in thermally annealed NiO/Si assembly

Present report details an analysis of X-ray reflectivity (XRR) for solution processed NiO thin films on Si (100) substrates. The films were annealed at 700–1,000 °C for 1 h in air. XRR data indicated growth of SiO₂ layer from ~8 nm at 700 °C to ~66 nm at 1,000 °C along with significant variation of electron density profile. X-ray photoelectron spectroscopy and X-ray diffraction studies were used as supporting studies for phase purity and oxidation states of the NiO thin films as well as interfacial SiO₂ layer.     

Atomic transport and chemical stability during annealing of ultrathin Al2O3 films on Si

Ultrathin films of Al2O3 deposited on Si were submitted to rapid thermal annealing in vacuum or in oxygen atmosphere, in the temperature range from 600 to 800 degrees C. Nuclear reaction profiling with subnanometric depth resolution evidenced mobility of O, Al, and Si species, and angle-resolved x-ray photoelectron spectroscopy revealed the formation of Si-Al-O compounds in near-surface regions, under oxidizing atmosphere at and above 700 degrees C. Under vacuum annealing all species remained essentially immobile. A model is presented based on diffusion-reaction equations capable of explaining the mobilities and reproducing the obtained profiles.     

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.     

Adsorption and reactions of HN3 on Si(1 0 0)-2 × 1: A computational study

We have studied the adsorption and decomposition of HN₃ on Si(1 0 0)-2 × 1 surface using the hybrid density functional B3LYP method and effective core potential basis, LanL2DZ, with Si₁₅H₁₆ as a double dimer surface model for cluster calculations. The result shows that the barriers for the dissociative adsorption of HN₃ forming HN(a) + N₂(g) are quite low by stepwise dissociation processes occurring either on a dimer or across the dimers. The low activation energies are consistent with previous experimental observations that the molecularly adsorbed HN₃(a) can undergo decomposition producing HN(a) at low surface temperatures. On the other hand, the predicted activation energies for the N₃(a) + H(a) formation processes are all relatively higher. These results also explain the absence of the N₃(a) species in HREELS measurements following each annealing experiment. Several selected reaction paths were also confirmed with slab model calculations using an optimization approach coupling the energy and gradient calculations by the slab model with the geometrical optimization using Berny algorithm.In addition, the adsorbate effect was examined for the end-on and side-on molecular configurations. For the side-on adsorption configuration, all possible combinations with 1-4 adsorbates can exist on the four surface Si sites of the double dimers, with adsorption energies lying closely to the multiples of that of a single side-on adsorbate (LM2); i.e., adsorption energies are nearly additive. Interestingly, for the end-on adsorption, only 1 and 2 HN₃ molecules can adsorb on a dimer due to the presence of the negative charges on the remaining Si sites in the neighboring dimer. For the two end-on adsorbates on the same dimer, the total adsorption energy is close to two times that of HN₃(a) or LM1. For the mixed end-on/side-on configurations, only one of each type can co-exist on a single dimer pair (Si₁-Si₂ or Si₃-Si₄) sites with adsorption energy close to the sum of those of one end-on and one side-on adsorbate. Finally, the predicted reaction routes and vibrational frequencies showed good agreement with previous experimental results. The stabilities of many ad-species involved in these reactions with end-on and/or side-on configurations have been predicted together with the transition states connecting those species.