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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 58 (1986), S. 601-607 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4421-4423 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We demonstrate that the surface structure of organic monolayers can be determined by low energy helium diffraction at low surface temperatures. This uniquely surface-sensitive and nondestructive technique shows that the CH3-terminated surface of a monolayer of docosane thiol (CH3(CH2)21SH) on Au(111) is composed of small, ordered domains (lattice constant 5.01±0.02 A(ring)), a large fraction of which share a common orientation. The helium diffraction intensities decrease monotonically with increasing temperature and vanish around 100 K, due to thermal motion of the CH3 groups. Surface order is observed for chains as short as ten carbons (CH3(CH2)9SH) but a shorter chain, (CH3(CH2)5SH), gave no diffraction.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8493-8502 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Low energy helium diffraction has been used to study the packing and thermal motion of the terminal CH3 groups of monolayers of n-alkane thiols self-assembled on Au(111)/mica films and a Au(111) single crystal surface. At low temperatures (〈100 K), the terminal CH3 groups are arranged in domains containing a hexagonal lattice with a lattice constant of 5.01 A(ring). As the length of the carbon chain is shortened, an abrupt decrease in the diffraction peak intensities is observed for CH3(CH2)9SH/Au(111)/mica, and no diffraction is observed for CH3(CH2)5SH/Au(111)/mica. This is indicative of a sudden decrease in surface order at around ten carbon atoms per chain. A semi-quantitative estimation of the average domain size of each monolayer surface shows a maximum of 46 A(ring) at intermediate chain length [CH3(CH2)13SH/Au(111)/mica], decreasing to 26 A(ring) at longer [CH3(CH2)21SH/Au(111)/mica] and 41 A(ring) at shorter [CH3(CH2)9SH/Au(111)/mica] chain lengths. No phase transitions could be detected at the surfaces of these monolayers from 35 K to 100 K, but as expected for a soft material, the thermal motion of the n-alkane thiol molecules increases with increasing surface temperature and reduces the diffraction intensities to zero at around 100 K. The relative mean square displacements of the surface CH3 groups along the directions perpendicular and parallel to the surface have been calculated from the temperature dependence of the diffraction peak intensities using the standard Debye–Waller formalism. The measured values are in good agreement with the results from a recent molecular dynamics simulation. [J. Hautman and M. Klein, J. Chem. Phys. 93, 7483 (1990).]
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 744-747 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present the results of a combined He atom and x-ray diffraction study of CH3(CH2)n−1SH monolayers self assembled on Au(111) surfaces. By combining these two complementary probes, we have characterized both the surface and the interior structure of the monolayers. In both cases, we find the same structure containing four molecules per unit mesh. However, we demonstrate that there are significant differences in both the diffraction linewidths and the dependence of the linewidth upon chain length for these two techniques.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3503-3511 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report direct evidence of a unit mesh containing more than one hydrocarbon chain at the surface of a self-assembled monolayer of long-chain n-alkanethiols. Our helium diffraction measurements for a monolayer of n-octadecanethiol on Au(111) are consistent with a rectangular primitive unit mesh of dimensions 8.68×10.02 A(ring) containing four crystallographically distinct hydrocarbon chains. This packing arrangement can also be described as a c(4×2) superlattice with respect to the fundamental simple hexagonal [((square root of)3×(square root of)3)R30°] array of lattice parameter 5.01 A(ring) previously observed for monolayers of other n-alkanethiols on gold. No temperature-dependent phase behavior is observed in the temperature range where surface diffraction is measurable (30–100 K) and cycling up to temperatures as high as 50 °C caused no observable change in the diffraction. It is proposed that this larger unit mesh is the result of a patterned arrangement of rotations of the hydrocarbon chains about their molecular axes. This patterned arrangement must be different than the herringbone structure expected by simple analogy to bulk n-alkanes.
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  • 6
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Low-energy helium diffraction has been used to study the surface structure, chain packing, and thermal vibrations of docosyl mercaptan [CH3(CH2)21SH] self-assembled on single crystal Au(111), (110), and (100). The docosyl mercaptan molecules form monolayers with different periodicity on the different surfaces of gold. On Au(111) at low temperatures (≤100 K), the terminal methyl groups of the docosyl mercaptan molecules form domains of a hexagonal lattice with a unit mesh constant of 5.01±0.02 A(ring). The sulfur head groups are arranged in a commensurate ((square root of)3×(square root of)3)R30° structure and are believed to adsorb on the triple hollow sites of the Au(111) lattice. The unit mesh parameters for CH3(CH2)21S/Au(110) are a=b=4.99±0.08 A(ring) and α=109.5°, suggesting that the chemisorbed sulfur atoms remove the "missing row'' reconstruction of the Au(110) surface and form a commensurate c(2×2) lattice. The adsorption of docosyl mercaptan molecules on a Au(100) surface results in a complicated diffraction pattern. Analysis of the data reveals an oblique unit mesh with a=b=5.97±0.09 A(ring) and α=95°±5° with four kinds of equivalent domains present because of the fourfold symmetry of Au(100). The above results confirm that the sulfur–substrate interaction plays an important role in determining the periodicity and the packing density of the molecules within the monolayers. The estimated average domain size of the terminal methyl groups is 22.8, 38.6, and 23.4 A(ring) for CH3(CH2)21SH self-assembled on Au(111), (110), and (100) faces, respectively. The chain packing and orientation within the unit cell are also discussed in this paper in conjunction with the latest results obtained via other techniques such as reflection IR spectroscopy and low-energy electron diffraction.
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  • 7
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 72 (1998), S. 133-133 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
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  • 8
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The bonding of alkyl monolayers to Si(111) surfaces has been studied by conventional x-ray photoelectron spectroscopy (XPS) and chemical-shift, scanned-energy photoelectron diffraction (PED) using synchrotron radiation. Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) olefin insertion into the H–Si bond on the H–Si(111) surface, and (ii) replacement of Cl on the Cl–Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, XPS has revealed a C 1s signal chemically shifted to lower binding energy, which we have assigned to carbon bonded to silicon. PED has shown that both preparative methods result in carbon bonded in an atop site with the expected C–Si bond length of 1.85±0.05 Å. Chemical-shift, scanned-energy photoelectron diffraction is a particularly valuable probe of local structure at surfaces that contain the same element in multiple, chemically distinct environments. © 1997 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 71 (1997), S. 1679-1681 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Dissolved oxygen in 40% aqueous ammonium fluoride solution initiates the formation of etch pits in the terraces of the otherwise ideal H-Si(111) surface. The etch pits are observed byex situ scanning tunneling microscopy in an argon atmosphere following emersion from the aqueous fluoride solution. Removal of O2from the fluoride solution by sparging with argon substantially reduces the initiation of etch pits. We propose the following mechanism of etch-pit initiation. Oxygen molecules are reduced to superoxide anion radicals at the negative open-circuit potential of the silicon surface. A small fraction (less than 0.4%) of these superoxide anions abstract hydrogen atoms from the H-Si(111) terraces to form silicon radicals (dangling bonds), which are then susceptible to etching in neutral to basic aqueous solutions. Hydrogen atom abstraction by aqueous superoxide anion radical also explains the known enhancement by water of oxide growth on hydrogen-terminated silicon surfaces. © 1997 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 72 (1998), S. 477-479 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Deuterium-terminated Si(111) surfaces are formed in a solution of KF and DCl in D2O. Infrared spectroscopy shows the surface to be flat with a D–Si bond normal to the surface. H–Si is formed preferentially to D–Si in a mixture of protonated and deuterated etchants. From the D-to-H exchange rate and the terrace width, we estimate the rate of the stepflow etching process to be 4.2 nm/s in Ar-sparged 40% NH4F solution. Dissolved O2 in the solutions substantially increases the D-to-H exchange rate by the formation of pits and the consequent increase in the step density. © 1998 American Institute of Physics.
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