Tin-oxide nanoparticles deposited from a beam: what happens to the composition?
Literature Information
M. Tchaplyguine, C. Wright, A. Shavorskiy, S. Zhu, M.-H. Mikkelä, C. Zhang, O. Björneholm, E. Mårsell, A. Mikkelsen, S. Sorensen, C. J. D. Hetherington, L. R. Wallenberg
The debate around the oxidation states occurring in laboratory-prepared tin-oxide samples has been for a long time an obstacle for an unambiguous assignment of characterization studies performed on such samples. In particular the changes in the Sn core-level energies caused by oxidation – i.e. the chemical shifts – as measured by photoelectron spectroscopy (PES) have been under discussion. The assignment problem is especially pronounced for nanoscale structures, which are important for photovoltaics, electronics, catalysis, and gas sensing. The reasons for the difficulties lie both in the natural properties of tin oxides, which can have substantial deficiencies of oxygen and tin in the lattice, and in the shortcomings of the fabrication and PES-characterization procedures themselves. Our recent PES study on tin-oxide nanoparticles fabricated by vapour-aggregation gave a chemical shift two times larger than earlier reported for Sn(IV) oxide for the Sn 4d level. The implemented fabrication technique forms an in-vacuum beam of particles whose composition can be both controlled and characterized by PES. In the present work SnO and SnO2 nanoparticles fabricated this way were deposited from the beam and probed by PES directly, as well as after exposure to air. The deposited nanoparticle films were also imaged by TEM (Transmission Electron Microscopy). The effects of the deposition process and exposure to air on the chemical composition were studied. The PES study of deposited SnO2 nanoparticles in the Sn 4d and Sn 3d core-level regions revealed the same core level shift as for unsupported nanoparticles, indicating that the chemical composition is preserved in the deposition process. The TEM study demonstrated a crystalline structure of separate SnO2 particles with lattice constants close to the macroscopic Sn(IV)-oxide. The PES study on the particles exposed to air showed changes in the composition. For the film of initially SnO particles a higher intermediate oxide was created. For the SnO2 nanoparticle film a lower, but strong, intermediate oxide was observed, likely at the surface.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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