Applied Surface Science 

Abstract: Chemical state X-ray photoelectron spectroscopic analysis of first row transition metals and their oxides and hydroxides is challenging due to the complexity of their 2p spectra resulting from peak asymmetries, complex multiplet splitting, shake-up and plasmon loss structure, and uncertain, overlapping binding energies. Our previous paper [M.C. Biesinger et al., Appl. Surf. Sci. 257 (2010) 887–898.] in which we examined Sc, Ti, V, Cu and Zn species, has shown that all the values of the spectral fitting parameters for each specific species, i.e. binding energy (eV), full wide at half maximum (FWHM) value (eV) for each pass energy, spin–orbit splitting values and asymmetric peak shape fitting parameters, are not all normally provided in the literature and data bases, and are necessary for reproducible, quantitative chemical state analysis. A more consistent, practical and effective approach to curve fitting was developed based on a combination of (1) standard spectra from quality reference samples, (2) a survey of appropriate literature databases and/or a compilation of literature references and (3) specific literature references where fitting procedures are available. This paper extends this approach to the chemical states of Cr, Mn, Fe, Co and Ni metals, and various oxides and hydroxides where intense, complex multiplet splitting in many of the chemical states of these elements poses unique difficulties for chemical state analysis. The curve fitting procedures proposed use the same criteria as proposed previously but with the additional complexity of fitting of multiplet split spectra which has been done based on spectra of numerous reference materials and theoretical XPS modeling of these transition metal species. Binding energies, FWHM values, asymmetric peak shape fitting parameters, multiplet peak separation and peak area percentages are presented. The procedures developed can be utilized to remove uncertainties in the analysis of surface states in nano-particles, corrosion, catalysis and surface-engineered materials.

Abstract: Samples of the iron oxides Fe0.94O, Fe3O4, Fe2O3, and Fe2SiO4 were prepared by high temperature equilibration in controlled gas atmospheres. The samples were fractured in vacuum and high resolution XPS spectra of the fractured surfaces were measured. The peak positions and peak shape parameters of Fe 3p for Fe2+ and Fe3+ were derived from the Fe 3p XPS spectra of the standard samples of 2FeO·SiO2 and Fe2O3, respectively. Using these parameters, the Fe 3p peaks of Fe3O4 and Fe1−yO are analysed. The results indicate that high resolution XPS techniques can be used to determine the Fe2+/Fe3+ ratios in metal oxides. The technique has the potential for application to other transition metal oxide systems.

Abstract: As one of the most appealing and attractive technologies, heterogeneous photocatalysis has been utilized to directly harvest, convert and store renewable solar energy for producing sustainable and green solar fuels and a broad range of environmental applications. Due to their unique physicochemical, optical and electrical properties, a wide variety of g-C3N4-based photocatalysts have been designed to drive various reduction and oxidation reactions under light irradiation with suitable wavelengths. In this review, we have systematically summarized the photocatalytic fundamentals of g-C3N4-based photocatalysts, including fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the design considerations of g-C3N4-based photocatalysts. The versatile properties of g-C3N4-based photocatalysts are highlighted, including their crystal structural, surface phisicochemical, stability, optical, adsorption, electrochemical, photoelectrochemical and electronic properties. Various design strategies are also thoroughly reviewed, including band-gap engineering, defect control, dimensionality tuning, pore texture tailoring, surface sensitization, heterojunction construction, co-catalyst and nanocarbon loading. Many important applications are also addressed, such as photocatalytic water splitting (H2 evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction, selective organic transformations and disinfection. Through reviewing the important state-of-the-art advances on this topic, it may provide new opportunities for designing and constructing highly effective g-C3N4-based photocatalysts for various applications in photocatalysis and other related fields, such as solar cell, photoelectrocatalysis, electrocatalysis, lithium battery, supercapacitor, fuel cell and separation and purification.

Abstract: The chemical state of oxygen, aluminum and zinc in Al-doped ZnO (ZAO) films was investigated by X-ray photoelectron spectroscopy (XPS), as well as the transition zone of the film-to-substrate, by auger electron spectroscopy (AES). The results show that zinc remains mostly in the formal valence states of Zn2+. A distinct asymmetry in Al 2p(3/2) photoelectron peaks has been resolved into two components, one is metallic Al and the other is oxidized Al. The depth profile of the two components revealed that metallic Al mainly exists in the thin surface layer. The close inspection of Ols shows that Ols is composed of three components, centered at 530.15 +/- 0.15, 531.25 +/- 0.20 and 532.40 +/- 0.15 eV, respectively. AES reveals an abrupt transition zone between the ZAO and quartz substrate. (C) 2000 Elsevier Science B.V. All rights reserved.

Abstract: We report on the resolution limits of Electron Beam Lithography (EBL) in the conventional polymethylmethacrylate (PMMA) organic resist. We show that resolution can be pushed below 10 nm for isolated features and how dense arrays of periodic structures can be fabricated at a pitch of 30 nm, leading to a density close to 700 Gbit/in2. We show that intrinsic resolution of the writing in the resist is as small as 3 to 5 nm at high incident electron energy, and that practical resolution is limited by the development of the resist after exposure and by pattern transfer. We present the results of our optimized process for reproducible fabrication of sub-10 nm lines by lift-off and 30-nm pitch pillar arrays by lift-off and reactive ion etching (RIE). We also present some applications of these nanostructures for the fabrication of very high density molds for nano-imprint lithography (NIL) and for the fabrication of Multiple Tunnel Junction devices that can be used for single electron device applications or for the connection of small molecules.