State selective enhanced production of excited fragments and ionic fragments of gaseous Si(CH3)2Cl2 and solid-state analogs following core-level excitation

State-selective fragmentation dynamics for excited fragments and ionic fragments of gaseous and condensed Si(CH3)2Cl2 following Cl 2p and Si 2p core-level excitations have been characterized. The Cl 2p-->15a1* excitation of Si(CH3)2Cl2 induces significant enhancement of the Cl+ desorption yield in the condensed phase and the Si(CH3)+2 and SiCH+3 yields in the gaseous phase. The core-to-Rydberg excitations at both Si 2p and Cl 2p edges lead to enhanced production of the excited fragments. These complementary results provide deeper insight into the origin of state-selective fragmentation of molecules via core-level excitation.     

Enhanced production of ionic photofragments of Si(CH3)2Cl2 following core-to-valence excitation

The state-selective positive-ion and negative-ion dissociation pathways for gaseous and condensed Si(CH₃)₂Cl₂ following the Cl 2p and Si 2p core-level excitations have been characterized using synchrotron radiation. The Si excitation of Si(CH₃)₂Cl₂ induces an enhancement of the Cl⁺ desorption yield in the condensed phase and the and yields in the gaseous-phase. The Cl⁻desorption yields are notably enhanced at the resonance at both Cl 2p and Si 2p edges. The resonant enhancement of Cl⁻ yield occurs through the formation of highly excited states of the adsorbed molecules. These results provide an insight into the comprehensive understanding of the state-selective fragmentation of molecules via core-level excitation.     

X-ray initiated molecular photochemistry of Cl-containing adsorbates on a Si(1 0 0) surface using synchrotron radiation

X-ray initiated molecular photochemistry for SiCl₄ and CCl₄ adsorbed on Si(1 0 0) at ∼90 K following Cl 2p core-level excitation is investigated by photon stimulated ion desorption and ion kinetic energy distribution measurements. The Cl excitation of solid SiCl₄ induces the significant enhancement (∼900%) of the Cl⁺ yield, while the Cl excitation of condensed CCl₄ leads to a moderate enhancement (∼500%) of the Cl⁺ yield. The enhancement of Cl⁺ yield at the specific core-excited states is strongly correlated to the ion escaped energy. Upon X-ray exposure for CCl₄ adsorbed on Si(1 0 0) (20-L exposure), the Cl⁺ yields at resonances decrease and new structures at higher photon energies are observed. Cl⁺ yields at these new resonances are significantly enhanced compared to those at other resonances. These changes are the results of desorption and surface reaction of the CCl₄-Si surface complex due to X-ray irradiation. We have demonstrated that state-specific enhancement of ion desorption can be successfully applied to characterize the reaction dynamics of adsorbates adsorbed on surfaces by X-ray irradiation.     

Core-level photoemission study of 2D ordered Bi/Si(100) interfaces

A high resolution core-level photoemission investigation of 2D ordered Bi layers grown on Si(100)-(2×1) is presented. We study the Si 2p and Bi 5d core-levels at room temperature as a function of coverage and in the reconstructed phases. The different Bi structural configurations around the monolayer coverage and in the (2×n)-reconstructed phase are derived from the core-level lineshape evolution. By following the Fermi level pinning, the presence of Bi-induced occupied electronic states close to the Si mid-gap is suggested.     

X-Ray Photoelectron Spectroscopy and Reflection High Energy Electron Diffraction of Epitaxial Growth SiC on Si（100） Using C60 and Si

The formation of silicon carbide upon deposition of C60 and Si on Si（100） surface at 850^o C is studied via x-ray photoelectron spectroscopy and reflection high energy electron diffraction （RHEED）. The C ls, O ls and Si 2p core-level spectra and the RHEED patterns indicate the formation of 3C-SiC.     

0(+)(gs) --> 2(+)(1) excitations in the mirror nuclei 32Ar and 32Si

We measured the strength of the 0(+)(gs)-->2(+)(1) excitations in the radioactive mirror nuclei 32Ar and 32Si using the techniques of intermediate-energy Coulomb excitation for 32Ar and inelastic proton scattering in inverse kinematics for 32Si. The 32Ar measurement, taken together with previously existing Coulomb excitation data for 32Si, yields the isoscalar and isovector multipole matrix elements for the 0(+)(1)-->2(+)(1) transition between T = 2 states in the A = 32 system. The proton scattering measurement for 32Si, when combined with the Coulomb excitation data for this nucleus, yields a ratio of neutron and proton matrix elements, M(n)/M(p), for 32Si.     

Laser-Induced Current Switching Observed in the Discharge Media of CF2Cl2-N2 and CH3Cl-N2

Switchings of discharge current induced by ArF and KrF laser pulses in the discharge media of CF2Cl2-N2 and CH3Cl-N2 were investigated using a negative point-to-plane discharge apparatus. The electron attachment rate constants of CF2Cl2 in buffer gases of N2 and Ar were measured by a parallel-plate drift-tube apparatus at various E/N, from which the dominant negative ions in the discharge media were inferred. The conductivity of the discharge medium is enhanced upon laser irradiation due to conduction electrons being produced from photoelectron-detachment of Cl-. From the dependence of the enhanced current on laser power, the photodetachment cross sections of Cl- in a given discharge condition were derived to be 2.5 × 10-17 cm2 at 193 nm and 1.0 × 10-17 cm2 at 248 nm. After the current enhancement, the current was greatly reduced as was observed in the discharge medium of CF2Cl2-N2, but not in CH3Cl-N2. The mechanism for the optically induced reduction of discharge current is discussed.     

Local atomic environment of Si suboxides at the SiO2/Si(111) interface determined by angle-scanned photoelectron diffraction

Local environments of Si suboxides at the interface between a thermally grown SiO2 film and Si(111) were studied by angle-scanned photoelectron diffraction. Si 2p core-level spectra containing chemically shifted components were recorded. The components were deconvoluted by least squares fitting and assigned to different Si oxidation states. The obtained diffraction patterns of the various suboxides exhibit different features. Comparison of these patterns with multiple scattering calculations including a multipole R-factor analysis shows that a simple chemical abrupt interface model describes well the environment of the suboxides and indicates ordered SiO2 close to the interface.     

Structural analysis of the SiO2/Si100 interface by means of photoelectron diffraction

The local environment of Si atoms at the interface between a thermally grown SiO2 film and Si(100) was studied by angle-scanned photoelectron diffraction. Experimental photoelectron diffraction patterns for each Si oxidation state were obtained from the results of least squares fitting on Si 2p core-level spectra. A comparison of the diffraction patterns with multiple-scattering calculations including an R-factor analysis was performed. An excellent agreement between experimental and simulated data was achieved within the proposed bridge-bonded interface model [Phys. Rev. Lett. 84, 4393 (2000)]].     

Low-energy D scattering from Cs and CsCl adsorbed on the Si(100)2 × 1 surface

On the basis of neutralization and inelastic scattering of low-energy D⁺ ions, the bond nature of Cs and CsCl adsorbed on the Si(100)2 × 1 surface has been investigated. In a low-coverage regime ( < 0.2 ML), Cs is adsorbed ionically on Si(100) and subsequent oxygen adsorption readily causes the ionic Cs---O bond. CsCl is dissociatively adsorbed on the surface in a low-coverage regime due to the preferential reaction of Cl with the Si dangling bond and the resultant Cs is ionically bonded to Si.     

IR absorption enhancement for ionized p -nitrobenzoic acid on silver island films epitaxially grown on the 7 × 7 reconstructed Si(111) surface

An enhanced infrared absorption is reported for p-nitrobenzoic acid (PNBA) adsorbed on molecular-beam-epitaxially grown silver films at room temperature on 7×7 reconstructed Si(111) substrates. Reflection high-energy electron diffraction reveals the formation of Ag(111) islands even for 82-monolayer-thick silver deposition on the substrate. The NO₂ symmetric stretch of the surface-ionized species (PNBA^-) is a maximum in intensity at a thickness of 64 monolayers and is one order of magnitude stronger than the same mode of PNBA deposited at a thickness of 5 nm on a Si wafer. Based on the change in film morphology and in light transmittance with silver film thickness, this absorption enhancement is ascribed to the excitation of transverse collective electron resonance of the silver islands. The thickness dependence of the enhancement and of the film morphology will be compared with those observed for silver films deposited on oxidized Si(111) substrates. PACS 61.14.Hg; 68.37.Hk; 78.30.-J     

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.     

Surface modification without desorption: recycling of Cl on Si(100)-(2 x 1)

We demonstrate chlorine-induced modification of Si(100)-(2 x 1) under conditions where Cl is recycled rather than desorbed as SiCl2. A dimer with 2 Cl atoms, 2SiCl, converts to SiCl2+Si, allowing the bare Si atom to escape onto the terrace. At temperatures below the desorption threshold, the SiCl2 unit decays through Cl diffusion, allowing the second Si atom to escape. The result is a dimer vacancy, terrace regrowth structures, and Cl that is able to participate in another pitting event. Access to this unexpected roughening pathway is controlled by the Cl concentration and temperature. This previously overlooked process represents an important component of Si(100) surface processing.     

Solid-phase epitaxy of CaSi2 on Si(1 1 1) and the Schottky-barrier height of CaSi2/Si(1 1 1)

Thin Ca films were evaporated on Si(1 1 1) under UHV conditions and subsequently annealed in the temperature range 200–650 °C. The interdiffusion of Ca and Si was examined by ex situ Auger depth profiling. In situ monitoring of the Si 2p core-level shift by X-ray photoemission spectroscopy (XPS) was employed to study the silicide formation process. The formation temperature of CaSi₂ films on Si(1 1 1) was found to be about 350 °C. Epitaxial growth takes place at T≥400 °C. The morphology of the films, measured by atomic force microscopy (AFM), was correlated with their crystallinity as analyzed by X-ray diffraction (XRD). According to measurements of temperature-dependent I–V characteristics and internal photoemission the Schottky-barrier height of CaSi₂ on Si(1 1 1) amounts to qΦ_Bn=0.25 eV on n-type and to qΦ_Bp=0.82 eV on p-type silicon.     

Properties of the SiO2/SiC interface investigated by angle resolved studies of the Si 2p and Si 1s levels and the Si KLL Auger transitions

Angle resolved photoemission studies of the Si 2p and Si 1s core levels and the Si KL_2,3L_2,3 Auger transitions from SiO₂/SiC samples are reported. Most samples investigated were grown in situ on initially clean and well ordered √3×√3 reconstructed 4H-SiC(0 0 0 1) surfaces but some samples were grown ex situ using a standard dry oxidation procedure. The results presented cover samples with total oxide thicknesses from about 5 to 118 Å. The angle resolved data show that two oxidation states only, Si⁺¹ and Si⁺⁴, are required to explain and model recorded Si 2p, Si 1s and Si KLL spectra.The intensity variations observed in the core level components versus electron emission angle are found to be well described by a layer attenuation model for all samples when assuming a sub-oxide (Si₂O) at the interface with a thickness ranging from 2.5 to 4 Å. We conclude that the sub-oxide is located at the interface and that the thickness of this layer does not increase much when the total oxide thickness is increased from about 5 to 118 Å.The SiO₂ chemical shift is found to be larger in the Si 1s level than in the Si 2p level and to depend on the thickness of the oxide layer. The SiO₂ shift is found to be fairly constant for oxides less than about 10 Å thick, to increase by 0.5 eV when increasing the oxide thickness to around 25 Å and then to be fairly constant for thicker oxides. An even more pronounced dependence is observed in the Si KLL transitions where a relative energy shift of 0.9 eV is determined.The relative final state relaxation energy ΔR(2p) is determined from the modified Auger parameter. This yields a value of ΔR(2p)=−1.7 eV and implies, for SiO₂/SiC, a “true” chemical shift in the Si 2p level of only ≈0.4 eV for oxide layers of up to 10 Å thick.     

Monochromatic soft-x-ray-induced reactions of CF2Cl2 adsorbed on Si(111)-7 × 7 studied by continuous-time photon-stimulated desorption spectroscopy near the F(1s) edge

Continuous-time core-level photon-stimulated desorption (PSD) spectroscopy was used to investigate the monochromatic soft x-ray photoreactions of CF(2)Cl(2) adsorbed on Si(111)-7 × 7 near the F(1s) edge (681-704 eV). Sequential F(+) PSD spectra were observed as a function of photon exposure at the CF(2)Cl(2)-covered surface (dose = 2.0 × 10(14) molecules cm(-2), ～0.75 monolayer). The F(+) PSD and total electron yield (TEY) spectra of solid CF(2)Cl(2) near the F(1s) edge were also measured. Both F(+) PSD and TEY spectra depict three features in the energy range of 687-695 eV, and are assigned to the excitations of F(1s) to (13a(1) + 9b(2))[(C-Cl)(?)], (7b(1) + 14a(1))[(C-F)?] antibonding and 5p Rydberg orbitals, respectively. Following the Auger decay process, two holes are created in the C-F bonding orbitals producing the 2h1e final state which results in the F(+) desorption. This PSD mechanism, responsible for the F(+) PSD of solid CF(2)Cl(2), is used to explain the first F(+) PSD spectrum in the sequential F(+) PSD spectra. The variation of spectral shapes in the sequential F(+) PSD spectra shows the consumption of adsorbed CF(2)Cl(2) molecules and the production of surface SiF species as a function of photon exposure. The photolysis cross section of the adsorbed CF(2)Cl(2) molecules by photons with varying energy (681-704 eV) is deduced from the sequential F(+) PSD spectra and found to be ～6.0 × 10(-18) cm(2).     

Spectroscopic studies of the βp and β2p decay of 23Si

²³Si isotopes have been produced as projectile fragments of a ³⁶Ar primary beam at 95 MeV/nucleon at the LISE3 spectrometer of GANIL. After implantation in a detector telescope, β-delayed one-proton and β-delayed two-proton emission has been observed. The main one-proton peaks are at (1.32±0.04)MeV, (2.40±0.04)MeV, and (2.83±0.06)MeV. The total decay energy for the β2p decay is (6.18±0.10)MeV for the decay to the ground state and (5.86±0.10)MeV for the decay to the first excited state in the daughter nucleus. However, energetically possible decays via βpα and β3p emission have not been identified. The spectra allowed us to determine the excitation energy of the isobaric analogue state in ²³Al. This enabled us to calculate the coefficients of the T = 5/2 isobaric multiplet mass equation for A = 23. The mass excess of the ²³Si ground state was deduced. This value is compared to different theoretical predictions. Additionally, we determined the branching ratios for the different decay branches. A half-life measurement yielded T_1/2 = (40.7±0.4)ms.     

Interaction of cobalt atoms with an oxidized Si(100)2 × 1 surface

The initial stages of oxidation of a Si(100)2 × 1 surface and the interaction of cobalt atoms with it were studied by core-level photoelectron spectroscopy. The study was carried out with cobalt coverages of up to 8 ML. Computer modeling of the spectra of photoexcited electrons revealed Co atom penetration under the silicon oxide layer, an effect observed even at room temperature. This process was shown to give rise to the disappearance of silicon interface phases at the oxide-layer-silicon boundary and to the formation of a more complex phase involving atoms of Co, O, and Si. After completion of the process, a Co-Si solid solution forms at the interface.     

Biological functionalization of the amine-terminated Si(100) surface by glycine

A peptide reaction of glycine on an amine-terminated Si(100) surface was investigated using C 1s, N 1s, O 1s, and Si 2p core-level spectroscopy, where the amine-terminated Si(100) surface was prepared using NH₃. In-situ thermal treatments at a mild temperature of 50 °C after the adsorption of glycine on a room-temperature amine-terminated Si(100) surface induced the peptide reaction between the carboxyl group of glycine and the amine group of the surface. This suggests that the amine-terminated Si(100) surface can be an excellent template for constructing a junction between a biomaterial and a Si surface using a dry process.     

Core-level photoemission of the Si(1 1 1)– -Ag surface using synchrotron radiation

The evolution of Si 2p core-level photoemission during a structural conversion from the Si (1 1 1)– -Ag to the Si(1 1 1)– -Ag superstructures induced by Ag adatoms adsorption at 140 K was studied using synchrotron radiation. The component from the top-layer Si-trimer atoms on the former surface was found to split into two components in the latter surface. The result is discussed in terms of a relaxation in some of the Si trimers induced by Ag adatoms sitting on the nearby Ag triangles of the -Ag substrate. The intensity ratio between the split components is a key to exclude some structure models proposed so far for the phases.