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Molecular-Level Processing and Chemical Properties of Functional Ceramic Materials

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (31 May 2022) | Viewed by 10380

Special Issue Editors


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Guest Editor
Institute of Research on Ceramics (IRCER, UMR CNRS 7315), European Ceramic Center, Limoges, France
Interests: precursor chemistry and processing; preceramic polymers; polymer-derived ceramics; porous components; nanocomposites; fibers and matrices
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Guest Editor
Inorganic and Materials Chemistry, University of Cologne, Institute of Inorganic Chemistry, Greinstraße 6, D-50939 Cologne, Germany
Interests: molecular precursor libraries; precursor-derived materials; nanostructured materials; chemical vapor deposition; atomic layer deposition; sol–gel; nanofibers and nanowires; batteries; photovoltaics; solar hydrogen

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Guest Editor
Institute for Materials Science, Technische Universität Darmstadt, Otto-Berndt-Str. 2, D-64287 Darmstadt, Germany
Interests: inorganic polymers; polymer-derived glasses and glass ceramics; polymer-based nanocomposites; polymer-derived ceramic nanocomposites; polymer processing
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The synthesis of ceramics derived from precursors has been recognized as a powerful strategy to access materials with controlled and adjustable compositions, microstructures, shapes/morphologies, and consequently property profiles. Thus, a careful design of tailored precursors and extensive knowledge about their shaping and thermochemical conversion into desired ceramics are of crucial importance for providing improved rational preparative concepts and for developing the functional properties of the materials. Thus, this field represents a challenging world of new opportunities and required skills and expertise from several disciplines. This Special Issue entitled “Molecular-Level Processing and Chemical Properties of Functional Ceramic Materials” focuses on the synthesis and processing of oxide and non-oxide ceramic materials with an emphasis on solution techniques, gas phase, and condensed phase syntheses. Synthesis methods such as polymer-derived ceramics (PDCs), sol–gel, solvothermal, molten salts, chemical vapor deposition (CVD), and atomic layer deposition (ALD) techniques will be outlined. Specific emphasis will be placed on but not limited by the following topics (i) ceramics manufacturing strategies such as those assisted by additive manufacturing, (ii) computational/analytical methods enabling in situ diagnostics and mechanistic insights into both precursor chemistry and thermochemical conversion, and (iii) the development of properties of ceramics in line with the energy, environment, and health domains.

Dr. Samuel Bernard
Prof. Dr. Sanjay Mathur
Dr. Emanuel Ionescu
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Advanced design and synthesis
  • Precursor chemistry
  • Sol–gel
  • Polymer-derived ceramics
  • Gas phase
  • Thin films
  • Nanostructured materials
  • Shaping
  • Characterization
  • Structure-based design
  • Structure–property relationship

Published Papers (3 papers)

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Research

16 pages, 3859 KiB  
Article
Vapor Phase Synthesis of SnS Facilitated by Ligand-Driven “Launch Vehicle” Effect in Tin Precursors
by Ufuk Atamtürk, Veronika Brune, Shashank Mishra and Sanjay Mathur
Molecules 2021, 26(17), 5367; https://doi.org/10.3390/molecules26175367 - 03 Sep 2021
Cited by 3 | Viewed by 2592
Abstract
Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. [...] Read more.
Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. We report here on the synthesis of a new heteroleptic molecular precursor containing (i) a thiolate ligand forming a direct Sn-S bond, and (ii) a chelating O^N^N-donor ligand introducing a “launch vehicle”-effect into the synthesized compound, thus remarkably increasing its volatility. The newly synthesized tin compound [Sn(SBut)(tfb-dmeda)] 1 was characterized by single-crystal X-ray diffraction analysis that verified the desired Sn:S ratio in the molecule, which was demonstrated in the direct conversion of the molecular complex into SnS thin films. The multi-nuclei (1H, 13C, 19F, and 119Sn) and variable-temperature 1D and 2D NMR studies indicate retention of the overall solid-state structure of 1 in the solution and suggest the presence of a dynamic conformational equilibrium. The fragmentation behavior of 1 was analyzed by mass spectrometry and compared with those of homoleptic tin tertiary butyl thiolates [Sn(SBut)2] and [Sn(SBut)4]. The precursor 1 was then used to deposit SnS thin films on different substrates (FTO, Mo-coated soda-lime glass) by CVD and film growth rates at different temperatures (300–450 °C) and times (15–60 min), film thickness, crystalline quality, and surface morphology were investigated. Full article
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12 pages, 2895 KiB  
Article
Photoactive Thin-Film Structures of Curcumin, TiO2 and ZnO
by Anish Philip, Ramin Ghiyasi and Maarit Karppinen
Molecules 2021, 26(11), 3214; https://doi.org/10.3390/molecules26113214 - 27 May 2021
Cited by 9 | Viewed by 3873
Abstract
Curcumin is known as a biologically active compound and a possible antimicrobial agent. Here, we combine it with TiO2 and ZnO semiconductors, known for their photocatalytic properties, with an eye towards synergistic photo-harvesting and/or antimicrobial effects. We deposit different nanoscale multi-layer structures [...] Read more.
Curcumin is known as a biologically active compound and a possible antimicrobial agent. Here, we combine it with TiO2 and ZnO semiconductors, known for their photocatalytic properties, with an eye towards synergistic photo-harvesting and/or antimicrobial effects. We deposit different nanoscale multi-layer structures of curcumin, TiO2 and ZnO, by combining the solution-based spin-coating (S-C) technique and the gas-phase atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques. As one of the highlights, we demonstrate for these multi-layer structures a red-shift in the absorbance maximum and an expansion of the absorbance edge as far as the longest visible wavelength region, which activates them for the visible light harvesting. The novel fabrication approaches introduced here should be compatible with, e.g., textile substrates, opening up new horizons for novel applications such as new types of protective masks with thin conformal antimicrobial coatings. Full article
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17 pages, 4117 KiB  
Article
Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides
by Felix Rosenburg, Benjamin Balke, Norbert Nicoloso, Ralf Riedel and Emanuel Ionescu
Molecules 2020, 25(24), 5919; https://doi.org/10.3390/molecules25245919 - 14 Dec 2020
Cited by 14 | Viewed by 2993
Abstract
The present work elaborates on the correlation between the amount and ordering of the free carbon phase in silicon oxycarbides and their charge carrier transport behavior. Thus, silicon oxycarbides possessing free carbon contents from 0 to ca. 58 vol.% (SiOC/C) were synthesized and [...] Read more.
The present work elaborates on the correlation between the amount and ordering of the free carbon phase in silicon oxycarbides and their charge carrier transport behavior. Thus, silicon oxycarbides possessing free carbon contents from 0 to ca. 58 vol.% (SiOC/C) were synthesized and exposed to temperatures from 1100 to 1800 °C. The prepared samples were extensively analyzed concerning the thermal evolution of the sp2 carbon phase by means of Raman spectroscopy. Additionally, electrical conductivity and Hall measurements were performed and correlated with the structural information obtained from the Raman spectroscopic investigation. It is shown that the percolation threshold in SiOC/C samples depends on the temperature of their thermal treatment, varying from ca. 20 vol.% in the samples prepared at 1100 °C to ca. 6 vol.% for the samples annealed at 1600 °C. Moreover, three different conduction regimes are identified in SiOC/C, depending on its sp2 carbon content: (i) at low carbon contents (i.e., <1 vol.%), the silicon oxycarbide glassy matrix dominates the charge carrier transport, which exhibits an activation energy of ca. 1 eV and occurs within localized states, presumably dangling bonds; (ii) near the percolation threshold, tunneling or hopping of charge carriers between spatially separated sp2 carbon precipitates appear to be responsible for the electrical conductivity; (iii) whereas above the percolation threshold, the charge carrier transport is only weakly activated (Ea = 0.03 eV) and is realized through the (continuous) carbon phase. Hall measurements on SiOC/C samples above the percolation threshold indicate p-type carriers mainly contributing to conduction. Their density is shown to vary with the sp2 carbon content in the range from 1014 to 1019 cm−3; whereas their mobility (ca. 3 cm2/V) seems to not depend on the sp2 carbon content. Full article
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