M. Hirsimäki

Oxygen adsorption-induced nanostructures and island formation on Cu{100}: Bridging the gap between the formation of surface confined oxygen chemisorption layer and oxide formation

Surface oxidation of Cu(100) has been investigated by variable temperature scanning tunneling microscopy and quantitative x-ray photoelectron spectroscopy as a function of O(2) pressure (8.0x10(-7) and 3.7x10(-2) mbar) at 373 K. Three distinct phases in the initial oxidation of Cu(100) have been observed: (1) the formation of the mixed oxygen chemisorption layer consisting of Cu(100)-c(2x2)-O and Cu(100)-(2sqrt[2]xsqrt[2])R45 degrees -O domains, (2) the growth of well-ordered (2sqrt[2]xsqrt[2])R45 degrees-O islands, and (3) the onset of subsurface oxide formation leading to the growth of disordered Cu(2)O. We demonstrate that the (2sqrt[2]xsqrt[2])R45 degrees-O reconstruction is relatively inert in the low pressure regime. The nucleation and growth of well-ordered two-dimensional Cu-O islands between two (2sqrt[2]xsqrt[2])R45 degrees-O domains is revealed by time-resolved scanning tunneling microscopy experiments up to 0.5 ML of oxygen. The formation of these islands and their nanostructure appear to be critical to the onset of further migration of oxygen atoms deeper into copper and subsequent Cu(2)O formation in the high pressure regime. The reactivity of each phase is correlated with the surface morphology and the role of the various island structures in the oxide growth is discussed.

Nanoscale oxidation of Cu(100): Oxide morphology and surface reactivity

Surface oxidation of Cu(100) in O(2) has been investigated in situ by x-ray photoelectron spectroscopy, x-ray induced Auger electron spectroscopy (XAES), and scanning tunneling microscopy (STM) as a function of surface temperature (T(S)=303-423 K) and O(2) pressure (p(O(2) )=3.7 x 10(-2)-213 mbars). Morphology of the oxide on the surface and in the near surface layers is characterized by utilizing STM and the inelastic electron background of the XAES O KLL signal. Analysis of the peak shape of the XAES Cu LMM facilitates the quantification of Cu, Cu(2)O, and CuO surface concentrations. The authors conclude that the surface oxidation of Cu(100) proceeds in three distinct steps: (1) Dissociative adsorption of O(2) and the onset of Cu-(2 square root 2 x square root 2)R45 degrees -O (theta(O)=0.5 ML) surface reconstruction, (2) initial formation of Cu(2)O and the appearance of 1.8 A high elongated islands that also adopt the Cu-(2 square root 2 x square root 2)R45 degrees -O structure, and (3) formation of highly corrugated Cu-O islands which together with the surface reconstruction strongly enhance the reactivity of the surface towards further oxide formation. Both Cu(2)O and CuO formations are enhanced by increased surface temperature, but no pressure dependence can be seen.

Instrumentation and analytical methods of an x-ray photoelectron spectroscopy–scanning tunneling microscopy surface analysis system for studying nanostructured materials

The design and performance of an x-ray photoelectron spectroscopy (XPS)–scanning tunneling microscopy (STM) surface analysis system for studying nanostructured materials are described. The analysis system features electron spectroscopy methods (XPS and Auger electron spectroscopy) in addition to a variable temperature STM. With the analytical methods of the system, surface chemical analysis as well as surface morphology down to atomic resolution can be obtained. The system also provides facilities for sample cleaning, annealing, gas dosing, depth profiling, and surface modifications by sputtering and evaporation. Controlled gas exposures from ultrahigh vacuum to atmospheric pressures in the adjustable temperature range of 120–1100K can be carried out in different chambers. A fast entry air lock allows the transfer of samples and STM tips into the system without air exposures. The surface analysis system uses a common sample holder in all five chambers which are independently pumped and separated from each...

Activated adsorption of methane on clean and oxygen-modified Pt{111} and Pd{110}

Abstract Activated adsorption of CH 4 on clean and oxygen modified Pt{111} and Pd{110} has been studied using molecular beam surface scattering. The absolute dissociation probability of CH 4 was measured as a function of the incident normal energy ( E ) and the surface temperature ( T s ). The results from clean Pt{111} and Pd{110} are consistent with a direct dissociation mechanism. The dissociative chemisorption dynamics of CH 4 is addressed by using quantum mechanical and statistical models. The influence of adsorbed oxygen on the dissociative adsorption of CH 4 on both Pt{111} and Pd{110} shows that the dissociation probability decreases linearly with increasing oxygen coverage.

Adsorption and thermal behavior of CO and NO on Pd{110} and Pd{320}

Chemisorption and thermal behavior of CO and NO on Pd{110} and its vicinal surface, Pd{320} [Pd(S)[3(110)×(100)]], have been investigated using molecular beam surface scattering (MBSS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). CO is shown to adsorb molecularly on Pd{320} in the temperature range of 250–500 K. No evidence for long-range ordering of CO adlayers on Pd{320} was observed. Saturation coverage for CO/Pd{320} at 300 K is 0.61 ML. The initial sticking probability of CO is 0.91 and is shown to depend only weakly on the surface temperature. It is also found that the initial sticking probability of CO on Pd{110} exhibits a strong dependence on the kinetic energy of CO molecules and the CO adsorption on Pd{320} may also exhibit this same behavior. CO desorbs molecularly from Pd{320} with desorption features near 390 and 500 K. NO is shown to adsorb molecularly below 420 K with a high initial sticking probability ...

Adsorption, desorption and surface reactions of CO and NO on Pd{320}

Adsorption, desorption and a surface reaction between coadsorbed CO and NO on a stepped Pd{320} (Pd (S)[3(110) x (100) )]) surface have been studied using molecular beam surface scattering (MBSS), temperature-programmed desorption/reaction (TPD/TPR) and X-ray photoelectron spectroscopy (XPS). CO adsorbs molecularly on Pd{320} with an initial sticking probability close to unity at 300 K. and reversibly desorbs upon heating according to the first-order desorption kinetics. NO adsorption on Pd{320} is molecular in the temperature range of 300-400 K as indicated by MBSS and XPS. NO desorbs molecularly in addition to the formation of relatively large amounts of N2 and N 2 O near 500 K. Coadsorbed NO and CO are observed to react upon heating to produce an extremely narrow TPR peak of CO2 at ∼470 K. The location and half-width of the CO 2 TPR peak are almost independent of the initial coverages of CO and NO, which indicates an autocatalytic behaviour of the NO CO reaction kinetics on Pd{320}.

Role of translational and vibrational energy in the dissociative chemisorption of methane on Pd{110}

Abstract Dissociative adsorption of methane has been investigated on Pd {1 1 0} by using molecular beam surface scattering. The initial sticking probability has been determined in the translational energy range of 7–95 kJ/mol and at selected vibrational energies from 300 to 700 K. The measured initial sticking probability is found to increase strongly with both translational and vibrational energy of CH4 molecules. The activation of the dissociative chemisorption of CH4 induced by the vibrational energy is shown to depend on the translational energy and is attributed to the excitation of the bending modes of the incident molecule. We have also performed molecular dynamics simulations to investigate the dissociation mechanism theoretically. The simulations clearly demonstrate that an efficient energy transfer occurs upon adsorption between the translational and vibrational energies of the incident CH4 molecule, which thereby facilitates the deformation of the molecular structure of CH4 resulting in dissociation.

Biofunctional hybrid materials: bimolecular organosilane monolayers on FeCr alloys

Hybrid organic-inorganic interfaces are the key to functionalization of stainless steel (SS). We present a solution-based deposition method for fabricating uniform bimolecular organosilane monolayers on SS and show that their properties and functionalities can be further developed through site-specific biotinylation. We correlate molecular properties of the interface with its reactivity via surface sensitive synchrotron radiation mediated high-resolution photoelectron spectroscopy (HR-PES) and chemical derivatization (CD), and we demonstrate specific bonding of streptavidin proteins to the hybrid interface. The method facilitates efficient growth of uniform bimolecular organosilane monolayers on SS under ambient conditions without the need to prime the SS surface with vacuum-deposited inorganic buffer layers. The obtained insights into molecular bonding, orientation, and behaviour of surface-confined organofunctional silanes on SS enable a new generic approach to functionalization of SS surfaces with versatile nanomolecular organosilane layers.

Improved antifouling properties and selective biofunctionalization of stainless steel by employing heterobifunctional silane-polyethylene glycol overlayers and avidin-biotin technology

A straightforward solution-based method to modify the biofunctionality of stainless steel (SS) using heterobifunctional silane-polyethylene glycol (silane-PEG) overlayers is reported. Reduced nonspecific biofouling of both proteins and bacteria onto SS and further selective biofunctionalization of the modified surface were achieved. According to photoelectron spectroscopy analyses, the silane-PEGs formed less than 10 Å thick overlayers with close to 90% surface coverage and reproducible chemical compositions. Consequently, the surfaces also became more hydrophilic, and the observed non-specific biofouling of proteins was reduced by approximately 70%. In addition, the attachment of E. coli was reduced by more than 65%. Moreover, the potential of the overlayer to be further modified was demonstrated by successfully coupling biotinylated alkaline phosphatase (bAP) to a silane-PEG-biotin overlayer via avidin-biotin bridges. The activity of the immobilized enzyme was shown to be well preserved without compromising the achieved antifouling properties. Overall, the simple solution-based approach enables the tailoring of SS to enhance its activity for biomedical and biotechnological applications.

Kinetic hindrance during the surface oxidation of Cu(100)–c(10×2)-Ag

The influence of c(10x2)-Ag superstructure on the oxidation kinetics and oxygen adsorption-induced nanostructures on Cu(100) has been investigated as a function of O(2) exposure at 373 K by employing scanning tunneling microscopy and x-ray photoelectron spectroscopy. The oxygen adsorption-induced segregation of Cu through the Ag overlayer is found to trigger agglomeration of Ag and subsequent formation of ordered oval-shaped nanosize metallic Ag islands separated by Cu(100)-(2 radical2x radical2)R45 degrees -O surface phase. As oxygen exposure is further increased, all Ag is eventually covered by oxidized Cu. The presence of Ag delays the completion of the fully reconstructed (2 radical2x radical2)R45 degrees -O surface and the nucleation and growth of Cu(2)O islands by limiting Cu diffusion toward the surface. Once Cu(2)O grows into the bulk deeper than buried Ag, the oxidation kinetics follow that of the unalloyed clean Cu(100) surface. Similar kinds of Cu-O nanostructures are found on both clean Cu(100) and Cu(100)-c(10x2)-Ag surfaces. Details of the morphology of the Ag structures and kinetic control of the surface oxidation mechanism on Cu(100)-c(10x2)-Ag are discussed.