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Peer-reviewedCC BYMolecules

Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides

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 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.

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BibTeX
@article{rosenburg2026effect,
  title = {{Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides}},
  author = {Felix Rosenburg and Benjamin Balke and Norbert Nicoloso and Ralf Riedel and Emanuel Ionescu},
  journal = {Molecules},
  year = {2026},
  month = oct,
  doi = {10.3390/molecules25245919},
  url = {https://hal.science/hal-05789774v1},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides
AU  - Felix Rosenburg
AU  - Benjamin Balke
AU  - Norbert Nicoloso
AU  - Ralf Riedel
AU  - Emanuel Ionescu
PY  - 2026
DA  - 2026/10/09
JO  - Molecules
DO  - 10.3390/molecules25245919
UR  - https://hal.science/hal-05789774v1
AB  - 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.
SN  - 1420-3049
ER  -