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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 2440-2446 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Surface infrared spectroscopy and density functional cluster calculations are used to study the thermal and atomic hydrogen-induced decomposition of water molecules on the clean Si(100)-(2×1) surface. We report the first observation of the Si–H bending modes associated with the initial insertion of oxygen into the dimer and backbonds of a silicon dimer. We find that, while one and two oxygen-containing dimers are formed almost simultaneously during the thermal decomposition of water on this surface, atomic H can be used to drive the preferential formation of the singly oxidized dimer. This work highlights the sensitivity of Si–H bending modes to the details of local chemical structure in an inhomogeneous system, suggesting that the combined experimental and theoretical approach demonstrated herein may be extremely useful in studying even more complex systems such as the hydrogenation of defects in SiO2 films. © 2000 American Institute of Physics.
    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 109 (1998), S. 8058-8061 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report herein the first direct experimental evidence of a nitric oxide dimer (NO)2 which is significantly perturbed from gas- and condensed-phase (NO)2 by bonding of one of the nitrosyls to a metal surface. Infrared reflectance absorbance spectroscopy of isotopically mixed overlayers is used to identify the formation of this species from NO adsorption on oxidized Mo(110) and to characterize it as a second-layer NO[ν(14NO)=1871 cm−1] bound to a surface nitrosyl [ν(14NO)=1728 cm−1], The spectroscopic signature of this species is a small (∼8 cm−1) splitting of ν(NO) of each of the nitrosyls upon isotopic mixing, rather than the appearance of three different frequencies for νs(NO) and νa(NO). The formation of such a dimer on oxidized Mo(110) does not result in N–N bond formation, in contrast to the evolution of both N3 and N2O via a dinitrosyl intermediate on the same surface. This result suggests that, on surfaces which interact strongly enough with NO to form chemisorbed nitrosyls stable above room temperature, N–N bond formation is favored by surface-bonding of both nitrosyls, rather than coupling via the weak N–N bond of a condensed-phase type (NO)2 dimer. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 6067-6074 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of methanol (CH3OH) are investigated on a range of oxygen overlayers on Mo(110), with θO from ∼0.5 to 〉1 ML, using a combination of vibrational spectroscopies and temperature-programmed reaction. Infrared spectroscopy identifies a common, tilted methoxy intermediate at high temperature on all overlayers studied; electron energy loss spectroscopy shows that this intermediate decomposes to deposit oxygen exclusively in high-coordination sites. While C–O bond scission to evolve gas-phase methyl radicals is the only reaction observed for methoxy on highly oxidized Mo(110), on the surface oxygen overlayers competition between dehydrogenation and methyl evolution is highly sensitive to oxygen coverage. The enhanced selectivity for hydrocarbon formation from methanol reaction on oxygen-modified Mo(110) relative to the clean surface is attributed to inhibition of dehydrogenation pathways rather than to marked changes in the C–O bond potential of methoxy. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 6432-6442 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The adsorption and subsequent reaction of nitric oxide (NO) on Mo(110) has been studied by temperature programmed reaction, electron energy loss, and infrared reflectance absorbance spectroscopies. The predominant reaction pathway for a saturated NO overlayer is dissociation to atomic nitrogen and oxygen; in fact, for low NO coverages, dissociation is the only reaction and largely takes place below 300 K. At NO coverages above 65% of θsat, evolution of N2O, N2, and NO is also observed at low temperature. Temperature programmed reaction of isotopically mixed overlayers demonstrates that N2O formation occurs via reaction of two intact NO molecules, suggestive of a dimeric surface intermediate. Electron energy loss and infrared spectroscopies identify three ν(NO) features which are assigned to three distinct species; the frequencies of the ν(NO) peaks in the infrared spectrum of a saturated 14NO overlayer at 100 K are 1860, 1821, and 1720 cm−1. The 1860 and 1720 cm−1 features are assigned to monomeric NO. Based on the infrared spectrum of a mixed overlayer of 14NO and 15NO, and on comparison to reference spectra of NO adsorbed on MoO3, the 1821 cm−1 peak is identified as νs(NO) of a surface dinitrosyl complex, i.e., two NO molecules bound to one Mo site. The weakly bound NO with the stretch frequency of 1860 cm−1 is associated with NO desorption, while the dinitrosyl leads to low-temperature N2 and N2O formation and some dissociation. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 87 (2000), S. 1322-1330 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The nature of the silicon oxide transition region in the vicinity of the Si/SiO2 interface is probed by infrared and x-ray photoelectron spectroscopies. The layer-by-layer composition of the interface is evaluated by uniformly thinning thermal oxide films from 31 Å down to 6 Å. We find that the thickness dependence of the frequencies of the transverse optical and longitudinal optical phonons of the oxide film cannot be reconciled by consideration of simple homogeneous processes such as image charge effects or stress near the interface. Rather, by applying the Bruggeman effective medium approximation, we show that film inhomogeneity in the form of substoichiometric silicon oxide species accounts for the observed spectral changes as the interface is approached. The presence of such substoichiometric oxide species is supported by the thickness dependence of the integrated Si suboxide signal in companion x-ray photoelectron spectra. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 77 (2000), S. 130-132 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: We report on growth and characterization of both epitaxial and amorphous films Gd2O3 of (cursive-epsilon=14) and Y2O3(cursive-epsilon=18) as the gate dielectrics for Si prepared by ultrahigh vacuum vapor deposition. The use of vicinal Si (100) substrates is key to the growth of (110) oriented, single-domain films in the Mn2O3 structure. Typical electrical leakage results are 10−3 A/cm2 at 1 V for single domain epitaxial Gd2O3 and Y2O3 films with an equivalent SiO2 thickness, teq of 15 Å, and 10−6 A/cm2 at 1 V for smooth amorphous Y2O3 films (cursive-epsilon=18) with a teq of only 10 Å. For all the Gd2O3 films, the absence of SiO2 segregation at the interface is established from infrared absorption measurements. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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