Chemisorbed Oxygen Atoms Research Articles

Direct Work Function Measurement Using in-situ Ambient Pressure X-ray Photoemission Spectroscopy and Its Application on Copper Oxidation Process.

The work function (WF) measurement plays a critical role in engineering energy materials and energy devices. However, the ultra-high vacuum (UHV) environments of photoemission method limit the practical application for absolute work function measurements of materials, especially under complex working conditions. To understand the energy level of materials under complex chemical environments, the in-situ measurements of work function is necessary in complex metal/semiconductor system for various application. In this paper, we describe the utilization of ambient pressure X-ray photoemission spectroscopy (APXPS) with utilization of low photon energy X-ray for absolute WF measurements at BL02B of the Shanghai Synchrotron Radiation Facility. We herein present the WF measurement during oxygen adsorption on Pt(111) and oxidation of Cu(111) in ambient oxygen environment as demonstration of the APXPS capability for WF measurement. After oxygen chemisorption on Pt and formation of Cu2O, the WF will increase. This is due to charge transfer from metal to chemisorbed oxygen atoms. After the formation of bulk Cu2O and CuO, the WF value almost remain at ~5.5 eV. We believe the direct measurement of absolute work function via APXPS could help bridge the gap between the physical properties and the surface chemical species for metal/semiconductor materials.

Surface recombination in Pyrex in oxygen DC glow discharges: mesoscopic modelling and comparison with experiments

Surface recombination in an oxygen DC glow discharge in a Pyrex (borosilicate glass) tube is studied via mesoscopic modelling and comparison with measurements of recombination probability. A total of 106 experimental conditions are assessed, with discharge current varying between 10 and 40 mA, pressure values ranging between 0.75 and 10 Torr, and fixed outer wall temperatures ( Tw ) of −20, 5, 25 and 50∘C . The model includes O+O and O+O2 surface recombination reactions and a Tw dependent desorption frequency. The model is validated for all the 106 studied conditions and intends to have predictive capabilities. The analysis of the simulation results highlights that for Tw=−20∘C and Tw=5∘C the dominant recombination mechanisms involve physisorbed oxygen atoms ( OF ) in Langmuir–Hinshelwood (L-H) recombination OF+OF and in Eley–Rideal (E-R) recombination O2+OF , while for Tw=25∘C and Tw=50∘C processes involving chemisorbed oxygen atoms ( OS ) in E-R O+OS and L-H OF+OS also play a relevant role. A discussion is taken on the relevant recombination mechanisms and on ozone wall production, with relevance for higher pressure regimes.

Ab initio calculations of the chemisorption of atomic H and O on Pt and Ir metal and on bimetallic Pt x Ir y surfaces

Abstract Understanding the chemisorption of atoms on precious metal surfaces is of substantial interest for the rational design of heterogeneous and electrochemical catalysts. In this study, we report density functional theory (DFT) investigations of the chemisorption of atomic H and O on bimetallic Pt x Ir y (111) surfaces for bifunctional anode catalyst materials in polymer electrolyte membrane (PEM) fuel cells. We found that for both adsorbates, the adsorption on the Pt(111) surface is in general less exothermic than on the Ir(111) surface. Our study has revealed that chemisorption on the bimetallic surfaces becomes more stable with increasing number of Ir surface atoms at the adsorption site. While for hydrogen atoms the ONTOP sites yield the most negative adsorption energies, the chemisorption of oxygen atoms appears to be most stable on the FCC sites for both the mono- and bimetallic surfaces. Using the ab initio thermodynamics approach, we calculated phase diagrams for the chemisorption of H and O atoms on these metal surfaces in order to transfer our findings to finite temperature and pressure conditions. Our theoretical results may provide an improved understanding of the hydrogen oxidation reaction (HOR) and oxygen evolution reaction (OER) on intermetallic Pt x Ir y (111) surfaces and may be helpful for the rational design of new bifunctional PEM fuel cell anode catalyst materials.

Nanolithography of the nanocorral structure of chemisorbed oxygen atoms on the graphitic lattice

Controlled atomic patterning is an attractive tool to fine tune properties of graphitic lattice. Several O-functionalized derivatives of graphitic lattice have been widely studied, e.g., graphene oxide, reduced graphene oxide, and functionalized carbon nanotubes. A controlled patterning of chemisorbed O atom is highly desired to fine tune physical and chemical properties, e.g., bandgap, conductivity, hydrophilicity, reactivity, etc. However, patterning of chemisorbed O on the graphitic lattice at the nanometer scale has not been reported. In this study, using scanning tunneling microscopy (STM), we manipulate chemisorbed O (epoxy) on the graphitic lattice, on demand, on the desired atom, on an atom-by-atom basis. We show that chemisorbed O can be desorbed when an energy exceeding the energy barrier for desorption (∼1.3 eV) is supplied as the bias voltage for imaging. This resulted in pristine, defect-free, and clean graphitic lattice at the site of desorption. Nanometer-scale patterns with resolution of oxygen-free regions surrounded by oxygen-rich regions could be achieved by scanning a pre-defined area. A distinct imaging effects was observed with low and high bias voltage-based scanning which is attributed to the local density of states of the O-functionalized graphitic lattice. Overall, the novel atomic-oxygen nanolithography of graphitic surface opens pathways for studying physicochemical properties of the functional groups in nanometer-scale confinement.

Unraveling energetics and states of adsorbing oxygen species with MoS2 for modulated work function.

MoS2 and related transition metal dichalcogenides (TMDs) have recently been reported as having extensive applications in nanoelectronics and catalysis because of their unique physical and chemical properties. However, one practical challenge for MoS2-based applications arises from the easiness of oxygen contamination, which is likely to degrade performance. To this end, understanding the states and related energetics of adsorbed oxygen is critical. Herein, we identify various states of oxygen species adsorbed on the MoS2 surface with first-principles calculations. We reveal a "dissociative" mechanism through which a physisorbed oxygen molecule trapped at a sulfur vacancy can split into two chemisorbed oxygen atoms, namely a top-anchoring oxygen and a substituting oxygen, both of which show no adsorbate induced states in the bandgap. The electron and hole masses show an asymmetric effect in response to oxygen species with the hole mass being more sensitive to oxygen content due to a strong hybridization of oxygen states in the valence band edge of MoS2. Alteration of oxygen content allows modulation of the work function up to 0.5 eV, enabling reduced Schottky barriers in MoS2/metal contact. These results show that oxygen doping on MoS2 is a promising method for sulfur vacancy healing, carrier mass controlling, contact resistance reduction, and anchoring of surface electron dopants. Our study suggests that tuning the chemical composition of oxygen is viable for modulating the electronic properties of MoS2 and likely other chalcogen-incorporated TMDs, which offers promise for new optoelectronic applications.

The initial oxidation of the 4H-SiC (0001) surface with C-related point defects: Insight by first-principles calculations

The initial oxidation of 4H-SiC (0001) surfaces with C-related point defects (SurfCD) is studied by using first-principles coupled with thermodynamics calculations to gain deeper insights into the effects of C-related point defects on the formation of SiO2 and SiO2/SiC interface. Three types of SurfCD, including a surface with C interstitial defect (SurfCi), a surface with antisite defect (SurfCsi) and a surface with C vacancy (SurfVc) are considered. The initial oxidation of SurfCD commences on the chemisorption of oxygen atoms at the bridge sites between the Si atoms adjacent to the C-related point defects. As the oxygen coverage increased, the effects of C-related point defects on the adsorption sites and energies of oxygen atoms, the diffusion of oxygen atoms and the interfacial lattice strain are elucidated. The thermodynamic diagrams of O/4H-SiC structures are performed to investigate the stability of surface during the actual oxidation conditions for SurfCi, SurfCsi and SurfVc. Thermodynamically stable intermediate structures are observed on these surfaces during the initial formation of SiO2, the 1 ML structures are the most stable; the Si dangling bonds, Si-O-C structure and C-clusters are observed in the 1 ML structures. Moreover, the evolution mechanisms and electronic properties of the defects are further investigated.

Effects of pre- and post-microwave annealing treatments on pGe MOS device

Effects of pre- and post- microwave annealing (MWA) treatment on electrical characteristics of p-type Ge substrate (pGe) metal-oxide-semiconductor (MOS) devices were investigated in this work. The physical mechanism was studied with an X-ray photoelectron spectroscopy analysis. The pre-MWA treatment, which is similar to conventional post oxidation annealing on interfacial layer (IL), can passivate the oxygen vacancy by chemisorbed oxygen. The excess chemisorbed oxygen atoms may be left at the interface between IL and high-k, which would induce more interface/oxide traps and form more unstable components in IL. The chemisorbed oxygen can be replaced with well-bonded oxygen by using a post-MWA treatment on high-k dielectric , instead of a conventional post deposition annealing. As a result, pGe MOS device with a double-MWA treatment exhibits low equivalent oxide thickness value (~0.65 nm), small frequency dispersion, low interface trap density, and excellent reliability characteristics without increasing the leakage current. The oxygen vacancy passivation and chemisorbed oxygen suppression with a double-MWA treatment are crucial for high performance Ge MOS device and monolithic 3D IC applications. • The effect of pre- and post- microwave annealing (MWA) treatment is compared. • Oxygen vacancy can be passivated by chemisorbed oxygen in pre MWA. • Excess chemisorbed oxygen can be replaced with well-bonded oxygen by post MWA. • A p-type Ge substrate capacitor can be improved by double MWA.

Unraveling the oxide layer on Mo2C as the active center for hydrogen evolution reaction

Large-scale production of hydrogen fuels via electrochemical water splitting requires efficient and cost-effective electrocatalysts. Molybdenum carbide (Mo2C), as a promising substitute for expensive Pt-based catalysts, exhibits outstanding electrocatalytic performance toward hydrogen evolution reaction (HER). Herein, by combining theoretical studies and experimental measurements, we systematically investigate the surface stability and HER activity of Mo2C. We demonstrate that the Mo2C(100) surface is oxidized under HER turnover condition, and the HER activity shows a positive correlation with the oxidation degrees of this surface. The Mo2C(100) surface covered by a monolayer of oxygen atoms is verified as the most stable surface structure, which derives the optimum HER activity, and thus the surface chemisorbed oxygen atoms are identified as the active sites. This study provides new insights into developing efficient electrocatalysts for HER based on Mo2C.

Room temperature oxidation of GaAs(110) using high translational kinetic energy molecular beams of O2 visualized by STM

This study examines the reactive surface dynamics of GaAs(110) oxidation with molecular oxygen at room temperature over a range of impinging kinetic energies. Visualization of the surface by scanning tunneling microscopy (STM) after exposures to O2 with kinetic energies of 0.4–1.2 eV provides morphological and kinetic data that were obtained utilizing a novel instrument that combines a supersonic molecular beam with an in-line, in-situ STM. Oxidation was found to proceed by two morphologically distinct, competing mechanisms: a spatially homogeneous process with randomly distributed chemisorbed oxygen atoms leading to layer-by-layer oxide growth, and a spatially heterogeneous process with oxides nucleating on structural surface defects and growing vertically and laterally with continued exposure. Both oxidation mechanisms exhibit enhanced reactivity with increasing kinetic energy. Only trace oxidation was observed with O2 kinetic energies below 0.7 eV; a rapid increase in the rate of oxidation from 1.0 to 1.2 eV was found with homogeneous and heterogeneous oxidation proceeding simultaneously until full surface coverage was reached. In addition, the relative rates of the two mechanisms appear to change with O2 kinetic energy: spatially homogeneous oxidation is expected to dominate at lower kinetic energies (<0.7 eV) while the heterogenous growth of oxide islands increasingly dominates with higher kinetic energies (≥1.0 eV). The results obtained in this study conclusively demonstrate that a heterogenous oxidation mechanism is activated on GaAs(110) at high O2 kinetic energies, and reveal that thin oxide layers can be achieved with higher efficiency at room temperature using molecular beams of oxygen. These results provide vital information about the morphological evolution of the surface in conjunction with the overall kinetics, and identify a controlled method of enhanced oxidation at moderate temperatures that could potentially improve abruptness at oxide interfaces and be used in the fabrication of GaAs semiconductor devices.

The Role of Oxygen Atoms on Excitons at the Edges of Monolayer WS2.

We clarify that the chemisorption of oxygen atoms at the edges is a key contributor to the frequently observed edge enhancement and spatial non-uniformities of photoluminescence (PL) in WS2 monolayers. Here we have investigated with momentum- and real-space nanoimaging of the chemical and electronic density inhomogeneity of WS2 flakes. Our finding from a large panoply of techniques together with density functional theory calculation confirms that the oxygen chemisorption leads to the electron accumulation at the edges. This facilitates the trion dominance of PL at the edges of WS2 flakes. Our results highlight and unravel the significance of chemisorbed oxygen at the edges in the PL emission and electronic structure of WS2, providing a viable path to enhance the performance of transition-metal-dichalcogenide-based devices.

Nanostructured Fe,Co-Codoped MoO3 Thin Films

Molybdenum oxide (MoO3) and Fe,Co-codoped MoO3 thin films obtained by spray pyrolysis have been in-depth investigated to understand the effect of Co and Fe codoping on MoO3 thin films. The effect of Fe and Co on the structural, morphological and optical properties of MoO3 thin films have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray analysis (EDAX), optical and photoluminescence (PL) spectroscopy, and electropyroelectric methods. The XRD patterns demonstrated the formation of orthorhombic α-MoO3 by spray pyrolysis. SEM characterization has shown an increase in roughness of MoO3 thin films by Fe and Co doping. Optical reflectance and transmittance measurements have shown an increase in optical band gap with the increase in Fe and Co contents. Thermal conductivity and thermal diffusivity of Fe,Co-doped MoO3 were 24.10–25.86 Wm−1K−1 and 3.80 × 10−6–5.15 × 10−6 m2s−1, respectively. MoO3 thin films have shown PL emission. Doping MoO3 with Fe and Co increases emission in the visible range due to an increase number of chemisorbed oxygen atoms. The photodegradation of an aqueous solution of methylene blue (MB) depended on the content of the codoping elements (Fe,Co). The results showed that a degradation efficiency of 90% was observed after 60 min for MoO3: Fe 2%-Co 1%, while the degradation efficiency was about 35% for the undoped MoO3 thin film.

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.

Improved quality of graphene in the absence of hydrogen in a low-temperature growth process using an alcohol precursor

We present the results of low-temperature growth of graphene on polycrystalline copper foil surfaces at 800 °C by using low-pressure chemical-vapor deposition of alcohol precursors. The structural quality of the graphene sample was found to depend significantly on the ambient conditions during the annealing and the growth processes. The improved quality of graphene grown in an oxidizing environment was found to be associated with a lower nucleation density, suggesting that chemisorbed oxygen atoms play a critical role in determining the quality of graphene.

(10, 10) Single walled carbon nanotube consisted of chemisorbed oxygen atoms as a promising supercapacitor electrode material: A first principles study

The effects of atomic oxygen chemisorption on the electronic structures and quantum capacitance of (10, 10) CNT have been studied in this article. The results indicated that the chemisorption on bonds aligned with nanotube axis is more favorable than other position. The most efficient configuration for enhancing quantum capacitance is the nanotube with oxygen atoms chemisorbed on axial bonds. Specifically, in water stability range, the quantum capacitance of (10, 10) CNT before and after chemisorption of six oxygen atoms (aligned with nanotube axis) were found to be 222.6 (anode) −117.6 (cathode) and 306.9 (anode) −217.2 (cathode) F/g, respectively.

Adsorption of O_{2} on Ag(111): Evidence of Local Oxide Formation.

The atomic structure of the disordered phase formed by oxygen on Ag(111) at low coverage is determined by a combination of low-temperature scanning tunneling microscopy and density functional theory. We demonstrate that the previous assignment of the dark objects in STM to chemisorbed oxygen atoms is incorrect and incompatible with trefoil-like structures observed in atomic-resolution images in current work. In our model, each object is an oxidelike ring formed by six oxygen atoms around the vacancy in Ag(111).

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

In this article, we propose a novel mechanism for the atomic-level processes that lead to oxide formation and eventually Pt dissolution at an oxidized Pt(111) surface. The mechanism involves a Pt extraction step followed by the substitution of chemisorbed oxygen to the subsurface. The energy diagrams of these processes have been generated using density functional theory and were analyzed to determine the critical coverages of chemisorbed oxygen for the Pt extraction and Oads substitution steps. The Pt extraction process depends on two essential conditions: (1) the local coordination of a Pt surface atom by three chemisorbed oxygen atoms at nearest-neighboring fcc adsorption sites; (2) the interaction of the buckled Pt atom with surface water molecules. Results are discussed in terms of surface charging effects caused by oxygen coverage, surface strain effects, as well the contribution from electronic interaction effects. The utility of the proposed mechanism for the understanding of Pt stability at bimetallic surfaces will be demonstrated by evaluating the energy diagram of a CuML/Pt(111) near-surface alloy.

Stability of atomic oxygen chemisorption on Pt-alloy surfaces

A density functional theory calculation is used to investigate the atomic oxygen (O) stability over platinum (Pt) and Pt-based alloy surfaces. Here, the stability is connected with the preferential adsorption sites for O chemisorptions and the adsorption energy. Thus, the interaction mechanism between atomic O and metal surfaces is studied by using charge transfer analysis. In this present paper, atomic structure and binding energy of oxygen adsorption on the Pt(111) are in a very good agreement with experiment and previous density functional theory calculations. Furthermore, we obtained that the addition of ruthenium (Ru) and molybdenum (Mo) on the pure Pt surface enhances the adsorption energy. Our charge transfer analysis shows that the largest charge transfer contributing to the metal-O bonding formation is observed in the case of O/PtRuMo surface followed by O/PtRu surface. This is in consistency with metal d-orbital characteristic, where Mo has much more empty d-orbital than Ru in correspondence to accept electrons from atomic oxygen. Copyright © 2016 John Wiley & Sons, Ltd.

Mechanical properties of phosphorene nanoribbons and oxides

Mechanical properties of phosphorene nanoribbons and oxides are investigated by using density functional theory. It is found that the ideal strength of nanoribbon decreases in comparison with that of 2D phosphorene. The Young's modulus of armchair nanoribbon has a remarkable size effect because of the edge relaxations. The analysis of the stress-strain relation indicates that, owing to chemisorbed oxygen atoms, the ideal strength and Young's modulus of 2D phosphorene oxide are greatly reduced along the zigzag direction, especially upon high oxidation ratios. In addition, strain and oxidation have significant impacts on phonon dispersion.

Nitrile hydration to amide in water: Palladium-based nanoparticles vs molecular catalyst

The catalytic performance of small Pd-nanoparticles (NPs) (2.0nm), partially covered by chemisorbed oxygen atoms, and of Pd-acetate, both stabilized by 2,2′-bipyridine-end functionalized poly(ethyleneglycol) monomethylether was compared in the selective hydration of nitriles to amide in water under mild reaction conditions (353K). Regardless of the nitrile substrate employed, the Pd-NP-based catalyst showed much higher normalized TON-values (i.e. refereeing to the amount of surface Pd atoms) compared to the Pd(II) macrocomplex, as far as the first catalytic run was considered. Deactivation of the Pd-NP-based catalyst was significant due to the formation of a hydroxide-water layer on the NPs’ surface.

Chemisorbed oxygen atom on the activation of C–H bond in methane: a Rh model study

The pre-adsorbed oxygen has little effect on the catalytic activity of methane dehydrogenation on Rh-ad-atom catalysts.