Torr O2 Research Articles

Reaction of Cl Atom with c-C5F8 and c-C5HF7: Relative and Absolute Measurements of Rate Coefficients and Identification of Degradation Products.

Partially and fully fluorinated olefins are a class of compounds with relatively short atmospheric lifetimes and low 100-year global warming potentials, compared to their saturated predecessors, which are used or considered as refrigerants, propellants, solvents, and other end-uses. The cyclic unsaturated compounds c-C5F8 and c-C5HF7 are currently under consideration as etching agents for the semiconductor industry. In this study, we expand on our previous work on the reaction of the OH radical with c-C5F8 and c-C5HF7 and report the rate coefficients, k, for the gas-phase reaction of the Cl atom with c-C5F8 and c-C5HF7 over a range of temperature (245-367 K) and pressure (100-200 Torr of He or N2 and 0 to 4.8 Torr O2) using a pulsed laser photolysis-resonance fluorescence (PLP-RF) technique. In addition, a relative rate (RR) technique, employing multiple reference compounds, was used to study the Cl atom reactions at 296 K, 100 and 630 Torr (N2 or air) total pressure. Reaction rate coefficients, k1, of the Cl atom reaction with c-C5F8 were found to be independent of pressure, over the pressure range used in this work, with k1(296 K), derived as an average of results from the PLP-RF and RR techniques being (1.07 ± 0.02) × 10-12 cm3 molecule-1 s-1 and k1(T) = (7.76 ± 0.73) × 10-13 × (exp[(98 ± 26)/T]) cm3 molecule-1 s-1, where the quoted error limits represent the 2σ data precision. Rate coefficients, k2, for the Cl atom + c-C5HF7 reaction were measured to be k2(296 K) = (4.61 ± 0.10) × 10-12 cm3 molecule-1 s-1 and k2(T) = (7.42 ± 0.89) × 10-13 × (exp[(540 ± 32)/T]) cm3 molecule-1 s-1. The Cl atom temporal profiles, observed with the PLP-RF technique, indicate that the Cl atom with c-C5F8 and c-C5HF7 reactions lead to adduct formation. The equilibrium constants for adduct formation were derived in this work, and a second-law analysis was used to obtain ΔH and ΔS values of -18.5 ± 0.4 kcal mol-1, -30.9 ± 1.2 cal K-1 mol-1, and -13.9 ± 0.5 kcal mol-1, -27.6 ± 1.1 cal K-1 mol-1 for the c-C5F8 and c-C5HF7 reactions, respectively. The Cl-initiated degradation of c-C5F8 and c-C5HF7 in the presence of O2 was studied and stable products were identified via infrared spectroscopy using experimental or theoretically derived spectra from our previous OH reaction work. For c-C5F8, FC(O)CF2CF2CF2C(O)F and FC(O)C(O)F were observed with molar yields of 0.80 and 0.10, respectively. For c-C5HF7, we observed the formation of HC(O)CF2CF2CF2C(O)F and HC(O)C(O)F with a combined molar yield of 0.72. Carbonyl difluoride, F2CO, was also a major product in the decomposition of c-C5F8 and c-C5HF7. The oxidation mechanism of the Cl-initiated degradation of c-C5F8 and c-C5HF7 is discussed. Based on the combined findings from this and our previous work, the atmospheric implications from the use of c-C5F8 and c-C5HF7 are presented.

Effect of electronegativity on electron surface scattering in thin metal layers

In situ transport measurements on 10-nm-thick epitaxial Cu(001), Co(001), and Rh(001) layers exhibit a characteristic increase in the sheet resistance ΔRs/Ro = 43%, 10%, and 4% when adding 4.0, 13.0, and 13.0 monolayers of Ti, respectively. Similarly, exposing these layers to 0.6 Torr O2 results in a 26%, 22%, and <5% increase in Rs. This suggests that adatoms on Cu and Co surfaces considerably disturb the surface potential, leading to diffuse electron scattering and a resulting resistance increase while these effects are negligible for Rh. A similarly small resistivity increase Δρ/ρ < 7% is measured during air exposure of 10-nm-thick epitaxial layers of electronegative metals including Ru, Rh, Ir, W, and Mo, while Δρ/ρ increases to 11%–36% for more electropositive metals including Cu, Ag, Co, Ni, and Nb. The Δρ for Ni, Co, and Nb is larger than what is expected for a complete transition from specular to diffuse surface scattering, indicating a breakdown of the semiclassical Fuchs–Sondheimer model, which needs to be replaced by a two-dimensional conductor description. The measured inverse correlation between electronegativity and Δρ/ρ suggests that the magnitude of the surface potential perturbation is the primary parameter affecting electron surface scattering in thin metal layers. More specifically, the charge transfer from electropositive metal surfaces to adatoms perturbs the surface potential and causes electron surface scattering and a resistance increase. Conversely, electronegative metals facilitate smooth surface potentials with specular electron reflection and a minimized resistance increase. They are, therefore, promising as conductors for highly scaled interconnect lines.

Absolute Absorption Cross-Section of the Ã←X˜ Electronic Transition of the Ethyl Peroxy Radical and Rate Constant of Its Cross Reaction with HO2

The absolute absorption cross-section of the ethyl peroxy radical C2H5O2 in the Ã←X˜ electronic transition with the peak wavelength at 7596 cm−1 has been determined by the method of dual wavelengths time resolved continuous wave cavity ring down spectroscopy. C2H5O2 radicals were generated from pulsed 351 nm photolysis of C2H6/Cl2 mixture in presence of 100 Torr O2 at T = 295 K. C2H5O2 radicals were detected on one of the CRDS paths. Two methods have been applied for the determination of the C2H5O2 absorption cross-section: (i) based on Cl-atoms being converted alternatively to either C2H5O2 by adding C2H6 or to hydro peroxy radicals, HO2, by adding CH3OH to the mixture, whereby HO2 was reliably quantified on the second CRDS path in the 2ν1 vibrational overtone at 6638.2 cm−1 (ii) based on the reaction of C2H5O2 with HO2, measured under either excess HO2 or under excess C2H5O2 concentration. Both methods lead to the same peak absorption cross-section for C2H5O2 at 7596 cm−1 of σ = (1.0 ± 0.2) × 10−20 cm2. The rate constant for the cross reaction between of C2H5O2 and HO2 has been measured to be (6.2 ± 1.5) × 10−12 cm3 molecule−1 s−1.

Vacuum ultraviolet enhanced atomic layer etching of ruthenium films

Vacuum ultraviolet (VUV) enhanced atomic layer etching (ALE) of thin (∼8 nm) Ru films is demonstrated. Oxidation half-cycles of 2–5 min VUV/O2 co-exposure are used to oxidize near-surface Ru to RuO2 at 1 Torr O2 and 100–150 °C. In situ x-ray photoelectron spectroscopy measurements indicate that RuO2 formation saturates after ∼5 min of VUV/O2 exposure at 100 and 150 °C. The depth of Ru oxidation is limited by the rate of oxidation and can be controlled with substrate temperature and exposure time. Etching half-cycles are performed by exposing the oxidized Ru film to HCOOH vapor at 0.50 Torr for 30 s isothermally, which results in the removal of the oxidized Ru layer. The amount of Ru removed per ALE cycle is determined by comparing ex situ x-ray reflectivity (XRR) measurements of the film before and after etching. When using 2 min VUV/O2 co-exposure, approximately 0.8 and 0.9 Å of Ru is etched per cycle at 100 and 150 °C, respectively. XRR and atomic force microscopy measurements indicate that the as-deposited and sputtered Ru film surface becomes smoother as ALE is performed. The etch rate decreases with ALE cycles and corresponds to a slowing oxidation rate, which is likely associated with the decrease in surface roughness. Density functional theory is used to study the adsorption of oxidants in a model Ru system, and nudged elastic band (NEB) calculations describe O diffusion into the Ru substrate by following an O “probe” atom as it moves between Ru(002) atomic planes with 0.50 monolayer (ML) O on the surface. NEB results reveal an approximate energetic barrier to diffusion, Ea, of 5.10 eV for O to move through the second and third atomic Ru layers when O, which can form an RuOx species, is subsurface. This Ea is in excess of the energetic gain of 4.23 eV in adsorbing an O atom to Ru(002) with 0.50 ML O. The difference in Ea and the adsorption energy likely contributes to the self-limiting nature of the oxidation and explains the observation that VUV/O2 co-exposure time must be increased to allow additional time for O diffusing into the subsurface as it overcomes the barrier to subsurface O diffusion. The self-limiting oxidation of Ru arising from VUV/O2 at low temperatures, in turn, enables an ALE process for Ru.

A Vacuum Ultraviolet-Enhanced Oxidation Mechanism for Pd: Near-Surface Oxidation for Atomic Layer Etching.

Density functional theory (DFT) is used to better understand the oxidation of Pd metal using vacuum ultraviolet (VUV) light co-exposed with O2, which is known to produce O and O3. The oxidation of Pd metal arising from O, O2, and O3 is assessed on bare Pd, Pd with a 0.25 monolayer of adsorbed atomic O, and Pd with increasing O incorporation into the substrate. DFT calculations are complemented experimentally by co-exposing 20 nm Pd films to 1 Torr of O2 and VUV photons (6.5 < hν < 11.3 eV) from a D2 lamp at temperatures ranging from 50 to 200 °C and times from 30 s to 40 min. Oxidation of Pd is characterized using in situ X-ray photoelectron spectroscopy. Co-exposures at 50 °C and 1 Torr O2 are performed with the Pd illuminated by the VUV light and shadowed from the VUV light in attempting to select for the oxidant that impinges on the Pd surface and causes oxidation. Results suggest that atomic O incident from the gas phase is responsible for oxidation of Pd, as no PdOx formation is observed for the same time period with the sample shadowed. Growth of PdOx via O diffusion is studied with the nudged elastic band method. Atomic O diffusion through Pd has an activation energy barrier of ∼2.87 eV with respect to a surface O. This decreases to ∼1.80 eV once the 0.25 monolayer of O occupies the surface. The extent of Pd oxidation is limited to the near-surface Pd region for all times and temperatures investigated. PdOx formation does not appear to exceed one to two atomic layers of Pd for conditions explored herein.

Engineering Nanoscale Interfaces of Metal/Oxide Nanowires to Control Catalytic Activity.

The interfacial effect between a metal catalyst and its various supporting transition metal oxides on the catalytic activity of heterogeneous catalysis has been extensively explored; engineering interfacial sites of metal supported on metal oxide has been found to influence catalytic performance. Here, we investigate the interfacial effect of Pt nanowires (NWs) vertically and alternatingly stacked with titanium dioxide (TiO2) or cobalt monoxide (CoO) NWs, which exhibit a strong metal-support interaction under carbon monoxide (CO) oxidation. High-resolution nanotransfer printing based on nanoscale pattern replication and e-beam evaporation were utilized to obtain the Pt NWs cross-stacked on the CoO or TiO2 NW on the silicon dioxide (SiO2) substrate with varying numbers of nanowires. The morphology and interfacial area were precisely determined by means of atomic force microscopy and scanning electron microscopy. The cross-stacked Pt/TiO2 NW and Pt/CoO NW catalysts were estimated with CO oxidation under 40 Torr CO and 100 Torr O2 from 200 to 240 °C. Higher catalytic activity was found on the Pt/CoO NW catalyst than on Pt/TiO2 NWs and Pt NWs, which indicates the significance of nanoscale metal-oxide interfaces. As the number of nanowire layers increased, the catalytic activity became saturated. Our study demonstrates the interfacial role of nanoscale metal-oxide interfaces under CO oxidation, which has intriguing applications in the smart design of catalytic materials.

Improvement in conductance modulation linearity of artificial synapses based on NaNbO3 memristor

A crystalline NaNbO3 (NN) film was deposited on the TiN/SiO2/Si (T-S) substrate at 300 °C by using the pulsed laser deposition method. The NN film that was annealed at 300 °C under 5 Torr O2 atmosphere displays a typical bipolar switching curve. Growth and dissociation of the oxygen vacancy filament is responsible for the switching property of this NN memristor. This NN memristor shows good biological synaptic properties, but displays a non-linear conductance modulation with the application of an identical pulse. The non-linear conductance modulation is related to the non-linear growth of the oxygen vacancy filament that is controlled by two growth mechanisms (the fast redox process and the slow oxygen ion diffusion process) with different growth rates. The NN memristor was annealed under 10 Torr N2 atmosphere to increase the number of oxygen vacancies, and it displayed improved conductance modulation linearity. The filament in this NN film can be grown linearly and the redox process became the main growth mechanism. Therefore, the conductance modulation linearity can be improved by increasing the number of oxygen vacancies, and this method can be applied to other memristors.

Absolute Infrared Absorption Cross Section of the Simplest Criegee Intermediate Near 1285.7 cm-1.

The ν4 fundamental of the simplest Criegee intermediate, CH2OO, has been monitored with high-resolution infrared (IR) transient absorption spectroscopy under total pressures of 4-94 Torr. This IR spectrum provides an unambiguous identification of CH2OO and is potentially useful to determine the number density of CH2OO in various laboratory studies. Here we utilized an ultraviolet (UV) and IR coupled spectrometer to measure the UV and IR absorption spectra of CH2OO simultaneously; the absolute IR cross section can then be determined by using a known UV cross section. Due to significant pressure broadening in the studied pressure range, we integrated the IR absorption spectra between 1285.2 and 1286.4 cm-1 (covering the Q branch), and then we converted this integrated absorbance to the absolute integral IR cross section of CH2OO (for the Q branch); its absolute value is (3.7 ± 0.6) × 10-19 cm·molecule-1 or 2.2 ± 0.4 km·mol-1. The whole rotational band (P, Q, and R branches) can be adequately simulated by using the precise spectroscopic parameters from the literature, yielding the absolute integral IR cross section (full ν4 band) to be 19.2 ± 3.5 km·mol-1. For a practical detection of CH2OO, this work also reports the peak cross section as a function of total pressure (4-94 Torr O2). At low pressure (≤4 Torr), where the pressure broadening is insignificant, the absorption cross section of the highest peak is (6.2 ± 0.9) × 10-18 cm2·molecule-1 (at the system line width of 0.004 cm-1 fwhm).

Physical Properties of (Na1- xK x)NbO3 Thin Film Grown at Low Temperature Using Two-Dimensional Ca2Nb3O10 Nanosheet Seed Layer.

A monolayer Ca2Nb3O10 (CNO) nanosheet was deposited on a Pt/Ti/SiO2/Si substrate using the Langmuir-Blodgett method. This monolayer CNO nanosheet with a (001) surface termination was used as a seed layer to reduce the growth temperature of the crystalline (Na1- xK x)NbO3 (NKN) film. The crystalline NKN film was preferentially grown along the [001] direction at 400 °C. The ferroelectric and piezoelectric properties of this NKN film were influenced by the postannealing atmosphere due to the variations in the amounts of oxygen vacancies in the NKN film. The crystalline NKN film annealed at 300 °C under 50 Torr O2 atmosphere showed promising ferroelectric and piezoelectric properties; εr of 303 and tan δ of 2.0% at 100 kHz, Ps of 15.3 μC/cm2, Pr of 11.7 μC/cm2, and Ec of 78 kV/cm, and d33 of 139 pm/V. This NKN film showed the lowest leakage current, which can be explained by the Schottky emission mechanism. The Schottky barrier heights of the Pt/NKN and NKN/CNO/Pt interfaces were calculated to be 0.97 and 0.28 eV, respectively. The results of this work suggest a new method to grow crystalline thin films at low temperatures by using metal-oxide nanosheets as the seed layer.

Structural transformation of h-BN overlayers on Pt(111) in oxidative atmospheres.

Interaction of hexagonal boron nitride (h-BN) with gases is of great importance for its properties and applications. In the present work, the structural changes of h-BN overlayers on Pt(111) in oxidative atmospheres including O2 and NO2 have been investigated by using low energy electron microscopy, Auger electron spectroscopy, X-ray photoelectron spectroscopy (XPS), and near ambient pressure XPS. We find that h-BN islands can be intercalated by oxygen in 10-6 Torr O2 at 200 °C, while oxygen intercalation of full layer h-BN around 200 °C requires near ambient pressure O2 (0.1 Torr) or such a strong oxidant as NO2 (10-6 Torr). h-BN overlayers can be etched away in the gases at much high temperatures, e.g. 800 °C. Upon mild oxidation in O2 or NO2 at temperatures of 400-450 °C, h-BN is transformed to boron oxide (BOx) overlayers, which can be converted back to h-BN by heating in NH3 at 800 °C.

Gold Corroles as Near-IR Phosphors for Oxygen Sensing.

The triplet state of gold(III) corroles is exploited for optical oxygen sensing. We report intense phosphorescence for gold(III) corroles in the near-IR, an optical window that is ideal for tissue transparency. Moreover, the triplet excited-state emission exhibits significant changes in intensity and lifetime over the 0-160 Torr O2 pressure range. This renders these compounds sensitive at biologically relevant pressures and overcomes the spectral limitations of palladium and platinum porphyrins for oxygen sensing in biology.

Structural Characterization of Atomic Layer Deposited Vanadium Dioxide

Vanadium dioxide (VO2) is a promising smart material particularly appealing for added functionality in both electronic and optical applications. We investigate the structure of VO2 films fabricated using atomic layer deposition (ALD) on c-Al2O3 substrates and the structure of the same VO2 films after an optimized anneal for 2 h at 585 °C in 10–5 Torr O2. Synchrotron-based grazing incidence X-ray diffraction (GIXRD) measurements revealed that the as-deposited ALD VO2 contains small crystalline inclusions of both V2O5 and VO. Ex situ annealing of the ALD VO2 film results in formation of mixed phase VO2 (predominantly M1 with indications of a small amount of M2), with a twinned monoclinic structure that is highly oriented and lattice matched to the c-Al2O3 substrate. Using in situ temperature-dependent measurements, the M1 and M2 components were shown to transition across different temperature ranges, which could account for the hysteretic behavior seen in these VO2 thin films. Additionally, these high-quali...

Active Phase of FeOx/Pt Catalysts in Low-Temperature CO Oxidation and Preferential Oxidation of CO Reaction

The interface between metal and reducible oxide has attracted increasing interest in catalysis. The FeOx–Pt interface has been a typical example, which showed remarkable activity for the preferential oxidation of CO (PROX) at low temperatures. However, model catalytic studies under vacuum conditions or in high-pressure O-rich environment at 450 K have reported two different active phases with iron in two different valence states, invoking a possible pressure gap. To identify the active phase for low-temperature CO oxidation and PROX, it is necessary to investigate the stability and activity of FeO/Pt(111) under the realistic reaction conditions. We thus conducted an in situ study on FeO/Pt(111) from ultrahigh vacuum to the atmospheric pressure of reactant gases. Our study shows FeO islands were easily oxidized in 1 Torr O2 to form the trilayer FeO2 islands. However, the presence of 2 Torr CO could prevent the oxidation of FeO islands and lead to CO oxidation at the FeO/Pt(111) interface. The FeO/Pt(111) s...

Intercalation-etching of graphene on Pt(111) in H2 and O2 observed by in-situ low energy electron microscopy

Graphene layers are often exposed to gaseous environments in their synthesis and application processes, and interactions of graphene surfaces with molecules particularly H2 and O2 are of great importance in their physico-chemical properties. In this work, etching of graphene overlayers on Pt(111) in H2 and O2 atmospheres were investigated by in-situ low energy electron microscopy. Significant graphene etching was observed in 10-5 Torr H2 above 1023 K, which occurs simultaneously at graphene island edges and interiors with a determined reaction barrier at 5.7 eV. The similar etching phenomena were found in 10-7 Torr O2 above 973 K, while only island edges were reacted between 823 and 923 K. We suggest that etching of graphene edges is facilitated by Pt-aided hydrogenation or oxidation of edge carbon atoms while intercalation-etching is attributed to etching at the interiors at high temperatures. The different findings with etching in O2 and H2 depend on competitive adsorption, desorption, and diffusion processes of O and H atoms on Pt surface, as well as intercalation at the graphene/Pt interface.

Mass spectrometric monitoring of oxidation of aliphatic C6-C8 hydrocarbons and ethanol in low pressure oxygen and air plasmas.

Experimental and theoretical studies on the oxidation of saturated hydrocarbons (n-hexane, cyclohexane, n-heptane, n-octane and isooctane) and ethanol in 28 Torr O2 or air plasma generated by a hollow cathode discharge ion source were made. Ions corresponding to [M + 15]+ and [M + 13]+ in addition to [M - H]+ and [M - 3H]+ were detected as major ions where M is the sample molecule. The ions [M + 15]+ and [M + 13]+ were assigned as oxidation products, [M - H + O]+ and [M - 3H + O]+ , respectively. By the tandem mass spectrometry analysis of [M - H + O]+ and [M - 3H + O]+ , H2 O, olefins (and/or cycloalkanes) and oxygen-containing compounds were eliminated from these ions. Ozone as one of the terminal products in the O2 plasma was postulated as the oxidizing reagent. As an example, the reactions of C6 H14+• with O2 and of C6 H13+ (CH3 CH2 CH+ CH2 CH2 CH3 ) with ozone were examined by density functional theory calculations. Nucleophilic interaction of ozone with C6 H13+ leads to the formation of protonated ketone, CH3 CH2 C(=OH+ )CH2 CH2 CH3 . In air plasma, [M - H + O]+ became predominant over carbocations, [M - H]+ and [M - 3H]+ . For ethanol, the protonated acetic acid CH3 C(OH)2+ (m/z 61.03) was formed as the oxidation product. The peaks at m/z 75.04 and 75.08 are assigned as protonated ethyl formate and protonated diethyl ether, respectively, and that at m/z 89.06 as protonated ethyl acetate. Copyright © 2016 John Wiley & Sons, Ltd.

A study of the O/Ag(111) system with scanning tunneling microscopy and x-ray photoelectron spectroscopy at ambient pressures

The interaction of O2 with the Ag(111) surface was studied with scanning tunneling microscopy (STM) in the pressure range from 10−9Torr to 1atm at room temperature and with X-ray photoelectron spectroscopy (XPS) up to 0.3Torr O2 in the temperature range from RT to 413K. STM images show that the Ag(111) surface topography is little affected in regions with large flat terraces, except for the appearance of mobile features due to oxygen atoms at pressures above 0.01Torr. In regions where the step density is high, the surface became rough under 0.01Torr of O2, due to the local oxidation of Ag. Various chemical states of oxygen due to chemisorbed, oxide and subsurface species were identified by XPS as a function of pressure and temperature. The findings from the STM images and XPS measurements indicate that formation of an oxide phase, the thermodynamically stable form at room temperature under ambient O2 pressure, is kinetically hindered in the flat terrace areas but proceeds readily in regions with high-step density.

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Hydrogen sensing behavior of Pt-coated mesoporous anodic titania

We report on excellent hydrogen sensing properties of a Pt/TiO2 system based on mesoporous titania grown by plasma electrolytic oxidation of a Ti metal substrate. The Pt phase is deposited onto the titania surface as an electrically continuous Pt nanomesh layer with an e-beam process. Resistive sensor response between the Pt and Ti terminals of the resultant structure is studied at room temperature for different partial pressures of H2 gas (0.003–3 Torr) and different source voltages (0.5–2.0 V). A maximum resistance effect, reaching four orders of the magnitude for 3 Torr H2 in 160 Torr O2 is obtained at the bias voltage 1.4 V, and a strong effect is detected for only 0.003 Torr, or 20 ppm H2 concentration. For voltages in the range 1.0–1.4 V, electrical conductance of the sample is about a linear function of the H2 partial pressure in the gas phase. Influence of the background atmosphere (O2, N2 and vacuum) and the effect of bias reversal were investigated also, leading to a conclusion that the sensing mechanism can be related to ionic transport in the TiO2 layer.

XPS study of cobalt doped TiO2 films prepared by pulsed laser deposition

Five percent Co‐doped TiO2 films have been prepared under an oxygen partial pressure from 10−6 to 10−4 Torr. The samples were stored for two weeks under ambient conditions prior to X‐ray photoelectron spectroscopy investigation. The X‐ray photoelectron spectra of Ti 2p and 3p, as well as X‐ray induced Auger electron spectrum Ti L3M23V all show evidence for Ti3+ at the surface of the film grown in 10−6 Torr O2 partial pressure. The curve fitted Ti 2p3/2 spectrum indicates a concentration of 6.5% Ti3+. The films grown in higher O2 pressure do not show Ti3+ state clearly. Surface‐enriched cobalt in Co2+ state has been noted. Such Co2+ enrichment can be removed by in‐situ annealing at 650 °C for 45 min resulting in elemental state cobalt at the annealed surface. The annealed film still shows Ti3+ state in the surface region but the concentration becomes lower. The Ti3+ concentration was lowered to the detection limit after the annealed sample was exposed to atmosphere for 30 min. The surface enrichment of cobalt may play some role in preventing the Ti3+ species in the uppermost surface layer from being quickly oxidized in atmosphere. Copyright © 2014 John Wiley &amp; Sons, Ltd.

Growth and Characterization of Crystalline Silica Films on Pd(100)

Silica films grown on Pd(100) were characterized by Auger electron spectroscopy, low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM). While no evidence of long-range order could be detected for films grown below 600 K, STM images of these films nevertheless revealed flat surfaces through which the step-terrace structure of the substrate could be seen. Annealing the films in 10–6 Torr of O2 above 975 K resulted in crystalline bilayers that produced hexagonal LEED patterns with a periodicity twice that of the substrate and with one of the overlayer close-packed directions paralleling Pd[011]. The extent of the crystalline domains was limited to typically five repeat units along two of the three close-packed directions of the film but was tens of repeat units long along the third. The lattice matching to the substrate expands the spacing in the bilayer on Pd(100) compared to bulk crystalline SiO2 and bilayers observed on other substrates; as a consequence, it is suggested that the...