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Sub-picosecond permittivity of carbon nitrides probed with terahertz spectroscopy: revealing high dielectric response and conductivity

Abstract:
Organic based semiconductor materials offer emerging and sustainable solutions for solar energy conversion technologies and electronics. However, knowledge of their intrinsic (photo)physical properties is often limited, especially the effect of dielectric properties (εr = ε′) on exciton separation and charge generation at sub-picosecond timescales, which corresponds to THz frequencies. Thus, THz Time Domain Spectroscopy (THz-TDS) is used to directly and accurately extract the complex permittivity (ε = ε′ + iε″) and THz conductivity (σTHz) of organic Carbon Nitrides (CNx) and other polymers and elucidate the influence of environmental humidities. Overall, the THz dielectric response ε′ of CNx surpasses other organic and even glycolated materials, and water. For the ionic and 2D carbon nitride K-PHI, complex permittivity ε was observed to be strongly humidity dependent, with both ε′ and σTHz doubling from dry to humid conditions (ε′ from ∼4 to 8, σTHz 75 to 150 S/m, respectively). When compared to other photocatalysts, the THz dielectric response of CNx and especially humid K-PHI is within range of well-known oxides such as TiO2 that can efficiently generate charges from excitons, due to low exciton binding energies resulting from high ε′. The importance of dielectric property characterization on functionally relevant frequencies is thus highlighted, especially in the THz gap (0.1 – 10 THz), to understand the photophysical behaviour of organic semiconductors, even in the presence of water and hydrated ions. Such THz complex permittivity determination may also be beneficial for exploring next generation photo(electro)catalysts, electronics or ionotronics, and for computational property predictions that often require knowledge of ultrafast photophysical properties.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1039/d5el00170f

Authors

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Role:
Author
ORCID:
0009-0009-5577-2423
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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry
Role:
Author
ORCID:
0000-0002-5428-4526
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Role:
Author
ORCID:
0000-0003-0843-6477
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Role:
Author
ORCID:
0000-0003-2619-2859
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Role:
Author
ORCID:
0000-0001-7244-678X


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Funder identifier:
https://ror.org/001aqnf71
Grant:
NE/S007415/1
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Funder identifier:
https://ror.org/03wnrjx87
Grant:
URF\R1\251843
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Funder identifier:
https://ror.org/0439y7842
Grant:
EP/Z536258/1


Publisher:
Royal Society of Chemistry
Journal:
EES Solar More from this journal
Publication date:
2026-02-06
Acceptance date:
2026-02-03
DOI:
EISSN:
3033-4063
ISSN:
3033-4063


Language:
English
Keywords:
Source identifiers:
3763272
Deposit date:
2026-02-16
ARK identifier:
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