Chemisorption of 1,1-dichloroethene on the Si(1 1 1)-7 × 7 surface

Chemisorption of 1,1-dichloroethene (Cl₂CCH₂) to a Si(1 1 1)-7 × 7 surface was studied by means of X-ray photoelectron spectroscopy using synchrotron radiation, recording chlorine 2p and carbon 1s spectra. For carbon 1s, spectral assignment of the chemisorbed species is based on quantum chemical calculations of chemical shifts in model compounds.The results confirm the identity of covalently bonded 1-chlorovinyl (-CClCH₂) and vinylidene (CCH₂) adspecies. Upon chemisorption at room temperature it was found that about one-third of the molecules break one C-Cl bond while about two-thirds of the adsorbates break two C-Cl bonds. We do not, however, find evidence for isomerization of CCH₂ to di-bonded vinylene (-CHCH-).     

Reaction of acetonitrile with the silicon(0 0 1) surface: A combined XPS and FTIR study

The adsorption of acetonitrile on the Si(0 0 1) surface has been investigated using X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). XPS and FTIR spectra indicate that adsorbed acetonitrile forms two correlated binding configurations, a CN species with a strong FTIR absorption at 1540 cm⁻¹ and a CCN (ketenimine) species that has a very strong FTIR absorption at 1952 cm⁻¹. The CCN FTIR peak at 1952 cm⁻¹ shows a striking polarization dependence, with the infrared transition dipole almost entirely in the plane of the sample and parallel to the SiSi dimer axis. Our data suggests that the primary CCN structure results from cleavage of two C-H bonds, forming a structure in which the N and terminal C atom are both linked to the surface. Temperature-dependent experiments help to elucidate the complicated reaction mechanism for acetonitrile adsorbing onto the Si(0 0 1) surface. Dosing at higher temperature increases the amount of CCN relative to CN species while heating leads to direct transformation of the CN to the CCN species. Our results indicate that previous studies, which considered only products formed by cleavage of a single C-H bond, have misidentified the primary ketenimine product. A reinterpretation of the earlier results, combined with data presented here, sheds new light onto the products and mechanism of interaction of acetonitrile with Si(0 0 1).     

A theoretical study of c-C5H8 adsorption on Ge (0 0 1)-2 × 1 and on dimer vacancies on the surface: Electronic structure and bonding

In this work we analyzed the geometry and the chemical interactions for c-C₅H₈ adsorption on Ge (0 0 1), using density functional theory calculations (DFT). We examined the changes in the atomic interactions using a slab model. We considered two cases, the cyclopentene adsorption on Ge(0 0 1) and on dimer vacancies on the surface. We found an average distance H-Ge, -C-Ge and C-Ge of 1.50, 1.70 and 1.65 Å, respectively, on dimer vacancies; and an average C-Ge distance of 2.05 Å on Ge-Ge dimer. We also computed the density of states (DOS) and the DOS weighted overlap populations (OPDOS) corresponding to C-C, C-Ge, C-H, and Ge-Ge bonds. During adsorption the main contribution are the CC double bond in both cases, and the next C and the H's belonging to this bonds in the case of adsorption on dimer vacancies. The orbital contribution includes participation of the 2p_y and 2p_z orbitals corresponding to unsaturated C atoms, 2p_z corresponding to side saturated C, and the 4p orbitals of Ge for the adsorption on dimer vacancies; 2s and 2p_z orbitals corresponding to double bond C atoms, 4s and 4p_z orbitals of Ge for the adsorption on Ge(0 0 1).     

DFT calculations of XPS/NEXAFS and IR spectra to elucidate the reaction products of acetonitrile with Si(0 0 1)-2 × 1

NEXAFS data [S. Rangan et al., Phys. Rev. B 71 (2005) 165319] and FTIR data [M.P. Schwartz, R.J. Hamers, Surf. Sci. 601 (2007) 945] apparently do not converge in the identification of the reaction products of acetonitrile (CH₃CN) with Si(0 0 1)-2 × 1 at room temperature. Using DFT calculations of core-excited/core-ionized spectra and of IR vibrational frequencies and intensities, we show the consistency of the body of experimental data. Three species are present on the surface in equivalent amounts, a CN moiety, a pendent CN and a CCN ketenimine submitted to a strong twist imposed by the Si bond directionality. More generally, the paper shows the usefulness of spectroscopic data simulations in the elucidation of complex surface chemistry problems.     

Resonant Auger spectroscopy study of charge transfer phenomena in N 1s core-excited acetonitrile adsorbates on Si(0 0 1)-2 × 1

Acetonitrile (CH₃CN) adsorbs on Si(0 0 1)-2 × 1 at room temperature under two forms, a cycloaddition-like adduct (Si-CN-Si) and a pendent cyano (Si-CH₂-CN) resulting from the decomposition of the molecule. Resonant Auger spectroscopy has been used to study the excited-state-dependent electron transfer from the N 1s core-excited molecular adsorbate to the silicon substrate, using the core-hole lifetime (∼6 fs) as an internal clock. It is shown that the π_CN^∗ NEXAFS state lies within the silicon bandgap because of a core-excitonic effect. Therefore no charge transfer of the excited electron to the substrate is observed. On the other hand the π_CN^∗ NEXAFS state is placed within the silicon conduction band. Excitation to this orbital leads to valence/Auger spectra in which both resonant and normal Auger contributions are observed. Therefore there is evidence for a charge transfer from the pendent CN to the silicon surface, on a timescale estimated to tens of femtoseconds.     

Conformational isomers of stilbene on Si(1 0 0)

Stilbene (1,2-diphenylethylene) has shown an intriguing isomerisation behavior and may serve as a model system for “molecular switches” incorporating a CC double bond. To evaluate the possible use of such molecules as molecular switches on semiconductor surfaces, the adsorption of cis- and trans-stilbene on Si(1 0 0) has been investigated. Identification of both isomers is achieved by differences in adsorption geometry as revealed by NEXAFS, and differences in electronic structure in the occupied and unoccupied molecular orbitals. For both isomers, bonding takes place via the CC double bond to the Si dimer atoms allowing for free movement of the aromatic rings, a necessary prerequisite for photoinduced isomerisation on the surface. Our experimental results agree well with theoretical calculations.     

The chemistry of C2 perfluoroalkyl iodide on the Cu(1 1 1) single crystal surface

The thermal chemistry of perfluoroethyl iodide (C₂F₅I) adsorbed on Cu(1 1 1) has been investigated by temperature-programmed reaction/desorption (TPR/D), reflection-absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). I 4d and F 1s XPS spectra show that dissociative adsorption of C₂F₅I to form the surface-bound perfluroethyl (Cu-C₂F₅) moieties occurs at very low temperature (T < 90 K), while the C-F bond cleavage in adsorbed perfluroethyl (Cu-C₂F₅) begins at ca. 300 K. XPS and TPR/D studies further reveal that the reactions of ^βCF₃^αCF_2(ad) on Cu(1 1 1) are strongly dependent on the surface coverage. At high coverages (?0.16 L exposure), the adsorbed perfluroethyl (Cu-C₂F₅) evolves, via α-F elimination, into the surface-bound tetrafluoroethylidene moieties (CuCF-CF₃) followed by a dimerization step to form octafluoro-2-butene (CF₃CFCFCF₃) at 315 K as gas product. The surface-bound (Cu-C₂F₅) decomposes preferentially, at low coverages (?0.04 L), via consecutive α-F abstraction to afford intermediate, trifluoroethylidyne (CuCCF₃), resulting in the final coupling reaction to yield hexafluoro-2-butyne (CF₃CCCF₃) at 425 K. However, at middle coverages (ca. 0.08-0.16 L exposure), the adsorbed perfluroethyl (Cu-C₂F₅) first experiences an α-F elimination and then prefers to loss the second F from β position to yield the intermediate of Cu-CF₂-CFCu (μ-η,η-perfluorovinyl), which may further evolve into hexafluorocyclobutene (CF₂CFCFCF₂) at 350 K through cyclodimerization reaction. Our results have also shown that the surface reactions to yield the products, CF₃CFCFCF₃ and CF₃CCCF₃, obey first-order kinetics, whereas the formation of CF₂CFCFCF₂ follows second-order kinetics.     

Chemistry of l-proline on Pd(1 1 1): Temperature-programmed desorption and X-ray photoelectron spectroscopic study

The surface chemistry of proline is explored on Pd(1 1 1) using a combination of temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Proline adsorbs on Pd(1 1 1) at temperatures of 250 K and below into second and subsequent layers prior to the saturation of the first layer, where approximately 70% of the adsorbed proline is present in its zwitterionic form. Molecular proline desorbs between ∼315 K and ∼333 K depending on coverage. When adsorbed at ∼300 K, only the first monolayer is formed, and the proline is present as zwitterions, oriented such that all of the carbons are detected equally by XPS. Proline decomposes by scission of the C-COO bond, where the carboxylate moiety desorbs as carbon monoxide and carbon dioxide, while the nitrogen-containing moiety desorbs as to HCN, and evolves pyrrole at ∼390 K, pyrrolidine at ∼410 K, and final species that desorbs at ∼450 K that cannot be unequivocally assigned but may be 2-butenenitrile (CH₃-CHCH-CN), 3-butenenitrile (CH₂CH-CH₂-CN), 2-methyl-2-propenenitrile (CH₂C(CH₃)-CN) or cyclopropanecarbonitrile.     

Site-blocking effects of preadsorbed H on Pt(1 1 1) probed by 1,3-butadiene adsorption and reaction

The influence of hydrogen coadsorption on hydrocarbon chemistry on transition metal surfaces is a key aspect to an improved understanding of catalytic selective hydrogenation. We have investigated the effects of H preadsorption on adsorption and reaction of 1,3-butadiene (H₂CCHCHCH₂, C₄H₆) on Pt(1 1 1) surfaces by using temperature-programmed desorption (TPD) and Auger electron spectroscopy (AES). Preadsorbed hydrogen adatoms decrease the amount of 1,3-butadiene chemisorbed on the surface and chemisorption is completely blocked by the hydrogen monolayer (saturation) coverage (θ_H = 0.92 ML). No hydrogenation products of reactions between coadsorbed H adatoms and 1,3-butadiene were observed to desorb in TPD experiments over the range of θ_H investigated (θ_H = 0.6-0.9 ML). This is in strong contrast to the copious evolution of ethane (CH₃CH₃, C₂H₆) from coadsorbed hydrogen and ethylene (CH₂CH₂, C₂H₄) on Pt(1 1 1). Hydrogen adatoms effectively (in a 1:1 stoichiometry) remove sites from interaction with chemisorbed 1,3-butadiene, but do not affect adjacent sites. The adsorption energy of coadsorbed 1,3-butadiene is not affected by the presence of hydrogen on Pt(1 1 1). The chemisorbed 1,3-butadiene on hydrogen preadsorbed Pt(1 1 1) completely dehydrogenates to H₂ and surface carbon upon heating without any molecular desorption detected, which is identical to that observed on clean Pt(1 1 1). In addition to revealing aspects of site blocking that should have broad implications for hydrogen coadsorption with hydrocarbon molecules on transition metal surfaces in general, these results also provide additional basic information on the surface science of selective catalytic hydrogenation of butadiene in butadiene-butene mixtures.     

Improvement and mechanism of interfacial adhesion in PBO fiber/bismaleimide composite by oxygen plasma treatment

The improved interfacial adhesion of PBO fiber-reinforced bismaleimide composite by oxygen plasma processing was investigated in this paper. After treatment, the maximum value of interlaminar shear strength was 57.5 MPa, with an increase of 28.9%. The oxygen concentration of the fiber surface increased, as did the surface roughness, resulting in improvement of the surface wettability. The cleavage and rearrangement of surface bonds created new functional groups OCO, NCO and NO, thereby activating the fiber surface. And long-time treatment increased the reaction degree of surface groups while destroyed the newly-created physical structures. The enhancement of adhesion relied primarily on the strengthening of chemical bonding and mechanical interlocking between the fiber and the matrix. The composite rupture planes indicated that the fracture failure shifted from the interface to the matrix or the fiber.     

An XPS study of pulsed plasma polymerised allyl alcohol film growth on polyurethane

The growth of highly functionalised poly allyl alcohol films by pulsed plasma polymerisation of CH₂CHCH₂OH on biomedical grade polyurethane has been followed by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Film thickness is observed to increase approximately linearly with plasma modification time, suggesting a layer-by-layer growth mode of poly allyl alcohol. Water contact angle measurements reveal the change in the surface free energy of wetting decreases linearly with plasma modification up to the monolayer point after which a constant limiting value of −24 mJ m⁻² was attained. Films prepared at 20 W plasma power with a duty cycle of 10 μs:500 μs exhibit a high degree of hydroxyl (OH) retention with minimal fragmentation of the monomer observed. Increasing the plasma power up to 125 W is found to improve OH retention at the expense of ether formation generating films close to the monomer stoichiometry. Duty cycle plays an important role in controlling both film composition and thickness, with longer off times increasing OH retention, while longer on times enhance allyl alcohol film growth.     

A photoelectron diffraction investigation of vanadyl phthalocyanine on Au(1 1 1)

Scanned-energy mode photoelectron diffraction using the O 1s and V 2p emission perpendicular to the surface has been used to investigate the orientation and internal conformation of vanadyl phthalocyanine (VOPc) adsorbed on Au(1 1 1). The results confirm earlier indications from scanning tunnelling microscopy that the VO vanadyl bond points out of, and not into, the surface. The VO bondlength is 1.60 ± 0.04 Å, not significantly different from its value in bulk crystalline VOPc. However, the V atom in the adsorbed molecule is almost coplanar with the surrounding N atoms and is thus pulled down into the approximately planar region defined by the N and C atoms by 0.52 (+0.14/−0.10) Å, relative to its location in crystalline VOPc. This change must be attributed to the bonding interaction between the molecule and the underlying metal surface.     

A selective [4 + 2]-like cycloaddition of α, β-unsaturated ketone on Si(1 1 1)-7 × 7

The interaction of ethyl vinyl ketone (EVK) with Si(1 1 1)-7 × 7 has been investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. The disappearance of both stretching vibrations of CH₂ (3099 cm⁻¹) and CO (1684 cm⁻¹) coupled with the appearance of new CC stretching mode (1660 cm⁻¹) in the HREELS spectra of chemisorbed EVK clearly demonstrates the direct involvement of conjugated CC and CO bonds to form a SiC¹H₂C²HC³(C⁴H₂C⁵H₃)OSi surface species via [4 + 2]-like cycloaddition in a highly selective manner. In addition, XPS studies show that the C1s binding energies of C¹/C² and C³ upon chemisorption display chemical downshifts of 0.8 eV and 2.2 eV, respectively, further confirming the proposed [4 + 2]-like cycloaddition reaction for the EVK/Si(1 1 1)-7 × 7 system. DFT theoretical calculations suggest that the proposed [4 + 2]-like cycloadduct is thermodynamically most favorable.     

Isomeric effects on room-temperature chemisorption and thermal evolution of iso-, cis- and trans-dichloroethylene on Si(1 1 1)7 × 7

The room-temperature adsorption and thermal evolution of iso-, cis- and trans-dichloroethylene (DCE) on Si(1 1 1)7 × 7 have been studied by vibrational electron energy loss spectroscopy and thermal desorption spectrometry (TDS). The presence of the Si-Cl stretch at 510 cm⁻¹ suggests that, upon adsorption, all three isomers dissociate via C-Cl bond breakage on the 7 × 7 surface to form mono-σ bonded chlorovinyl , which could, in the case of iso-DCE, further dechlorinate to vinylidene (:CCH₂) upon insertion into the back-bond. The higher saturation exposure for the Si-Cl stretch at 510 cm⁻¹ observed for cis- and trans-DCE than iso-DCE suggests that Cl dissociation via the CHCl group in the cis and trans isomers is less readily than the CCl₂ group in iso-DCE. Our TDS data show remarkable similarities in both molecular desorption near 360 K and thermal evolution of the respective adstructures for all three isomers on Si(1 1 1)7 × 7. In particular, upon annealing to 450 K, the mono-σ bonded chlorovinyl adspecies is found to further dechlorinate to either vinylene di-σ bonded to the Si surface or acetylene to be released from the surface. Above 580 K, vinylene could also become gaseous acetylene or undergo H abstraction to produce hydrocarbon or SiC fragments. All three DCE isomers also exhibit TDS features attributable to an etching product SiCl₂ at 800-950 K and recombinative desorption products HCl at 700-900 K and H₂ at 650-820 K. The stronger Cl-derived TDS signals and Si-Cl stretch at 510 cm⁻¹ over 450-820 K for trans-DCE than those for cis-DCE indicate stronger dechlorination for trans-DCE than cis-DCE, which could be due to less steric hindrance resulting from the formation of the chlorovinyl adspecies for trans-DCE during the initial adsorption/dechlorination process. Finally, our density functional calculations qualitatively support the thermodynamic feasibility and relative stabilities of the proposed adstructures involving chlorovinyl, vinylidene, and vinylene adspecies.     

Hydrogen related point defects in silicon based layers: Si(·)H and SiOOH

Layers prepared by pulsed TEA CO₂ pulsed laser ablation (PLA) of SiO and SiO₂ targets in helium were exposed to hydrogen and deuterium atmosphere up to several kPa. The deposited layers were investigated by FTIR, EPR and XP spectroscopy. Among various Si species silyl radical Si(·)H (Si(·)D) at 2166 (1568) cm⁻¹—H(I) center—and silyl hydroperoxide SiOOH (SiOOD) at 3587 (2648) cm⁻¹ were identified in FTIR spectra. Chemical pathways for production of these species are discussed. Experimental results are supported by quantum chemical calculations.     

Ab initio studies of electronic spectra of the linear aluminum-bearing carbon chains AlC2nH (n = 1-5)

Geometries and stabilities of the linear aluminum-bearing carbon chains AlC_2nH (n = 1-5) in their ground states have been explored by the DFT-B3LYP and RCCSD(T) methods. Structures of the X¹Σ⁺ and 1¹Π electronic states have also been optimized by the CASSCF approach. The studies indicate that these species have single-triple bond alternate pattern, AlCCCC?CCH, and the electronic excitation from X¹Σ⁺ to 1¹Π leads to the shortening of the AlC bonds. The vertical excitation energies of the 1¹Π ← X¹Σ⁺ and 2¹Π ← X¹Σ⁺ transitions for AlC_2nH (n = 1-5) have been investigated by the CASPT2, EOM-CCSD, and TD-B3LYP levels of theory with the cc-pVTZ basis set, respectively. CASPT2-predicted 1¹Π ← X¹Σ⁺ transition energies are 3.57, 3.44, 3.33, 3.26, and 3.21 eV, respectively. For AlC₂H, our estimate agrees very well with the experimental value of 3.57 eV. In addition, the AlC bond dissociation energies and the exponential-decay curves for these vertical excitation energies are also discussed.     

Surface reactions of 2-iodopropane on GaAs(1 0 0)

The surface reactions of 2-iodopropane ((CH₃)₂CHI) on gallium-rich GaAs(1 0 0)-(4 × 1), was studied by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). CH₃CHICH₃ adsorbs molecularly at 120 K but dissociates below room temperature to form chemisorbed 2-propyl ((CH₃)₂CH) and iodide (I) species. Thermal activation causes desorption of the molecular species at 240 K, and this occurs in competition with the further reactions of the (CH₃)₂CH and I chemisorbed species. Self-coupling of the (CH₃)₂CH results in the formation of 2,3-dimethylbutane ((CH₃)₂CH-CH(CH₃)₂) at 290 K. β-Hydride elimination in (CH₃)₂CH yields gaseous propene (CH₃CHCH₂) at 550 K while reductive elimination reactions of (CH₃)₂CH with surface hydrogen yields propane (CH₃CH₂CH₃) at 560 K. Recombinative desorption of the adsorbed hydrogen as H₂ also occurs at 560 K. We observe that the activation barrier to carbon-carbon bond formation with 2-propyls on GaAs(1 0 0) is much lower than that in our previous investigations involving ethyl and 1,1,1-trifluoroethyl species where the β-elimination process was more facile. The difference in the surface chemistry in the case of 2-propyl species is attributable to its rigid structure resulting from the bonding to the surface via the second carbon atom, which causes the methyl groups to be further away from the surface than in the case of linear ethyl and 1,1,1-trifluoroethyl species. The β-hydride and reductive elimination processes in the adsorbed 2-propyl species thus occurs at higher temperatures, and a consequence of this is that GaI desorption, which is expected to occur in the temperature range 550-560 K becomes suppressed, and the chemisorbed iodine leaves the surface as atomic iodine.     

Effect of defects on the reflectivity of Cr/C multilayer soft X-ray mirror at 4.48 nm

Cr/C is a promising material combination for multilayer mirror in the “near water window region” (4.4-6.7 nm). In the present paper, the effect of defects on the reflectivity of Cr/C soft X-ray multilayer mirror deposited by magnetron sputtering was studied. Formation of thin interlayer due to the interdiffusion, rough interface due to the non-sharp layer and contamination of O happened during the deposition process were found by a method combined by XPS, soft X-ray reflectivity at 4.48 nm and grazing incidence hard X-ray reflectivity at 0.154 nm. The XPS results show that both interlayers (Cr-on-C and C-on-Cr) are mixture composed of C sp2, C sp3, CO, CO, CrCr and CrO bondings. No chromium carbide was found at the interlayer probably due to the blocking of oxides’ formation. Through the analysis of X-ray reflectivity, we obtained the multilayer structure parameters (thickness and roughness) and optical constants of each layer at 4.48 nm. Based on those results, a further calculation was carried out. The result shows that the formation of the thin interlayer contributes little to the decrease of the reflectivity, the rough interface decreases the reflectivity most and the contaminant (O) not only decreases the reflectivity but also shifts the position of the peak.     

S180 cell growth on low ion energy plasma treated TiO2 thin films

X-ray photoelectron spectroscopy (XPS) was used to characterise the effects of low energy (<2 eV) argon ion plasma surface modification of TiO₂ thin films deposited by radio frequency (RF) magnetron sputter system. The low energy argon ion plasma surface modification of TiO₂ in a two-stage hybrid system had increased the proportion of surface states of TiO₂ as Ti³⁺. The proportion of carbon atoms as alcohol/ether (COX) was decreased with increase the RF power and carbon atoms as carbonyl (CO) functionality had increased for low RF power treatment. The proportion of C(O)OX functionality at the surface was decreased at low power and further increase in power has showed an increase in its relive proportion at the surface. The growth of S180 cells was observed and it seems that cells are uniformly spreads on tissue culture polystyrene surface and untreated TiO₂ surfaces whereas small-localised cell free area can be seen on plasma treated TiO₂ surfaces which may be due to decrease in C(O)OX, increase in CO and active sites at the surface. A relatively large variation in the surface functionalities with no change in the surface roughness was achieved by different RF plasma treatments of TiO₂ surface whereas no significant change in S180 cell growth with different plasma treatments. This may be because cell growth on TiO₂ was mainly influenced by nano-surface characteristics of oxide films rather than surface chemistry.