Details
| Original language | English |
|---|---|
| Article number | 109078 |
| Journal | Journal of Physics and Chemistry of Solids |
| Volume | 135 |
| Early online date | 26 Jun 2019 |
| Publication status | Published - Dec 2019 |
Abstract
We propose a ring substitution as a method of modulation of optoelectronic properties of organo-metal halide perovskites containing unsaturated heterocyclic cations. Periodic DFT calculations of tin trichloride perovskites with arizinium cation and its derivatives show that an introduction of the electron-withdrawing –C[tbnd]N and –F groups into azirinium ring stabilizes the materials' CBs formed from antibonding molecular π-orbitals of the ring. This leads to a decrease of the perovskite bandgaps as compared to that of the parent arizinium tin trichloride (1.06 eV). The effect of the electron-donating groups –CH 3 and –NH 2 on the materials’ CBs and bandgaps is opposite. The predicted bandgaps of the four perovskites cover the energy range of [0.52:1.93] eV. A combination of both electronic effects in one ring substituent allows for a finer tuning of the perovskite optoelectronic properties that is exemplified by fluorinated methylarizinium tin trichlorides. Bandgaps of these materials vary from 1.86 eV (R = -CH 3) to 1.17 eV (R = -CF 3). Thus, a ring substitution in unsaturated heterocyclic cations of organo-metal halide perovskites paves a way to modulating their optoelectronic properties in a wide energy range.
Keywords
- DFT, Electronic properties, Optical absorption, Organo-metal halide perovskites
ASJC Scopus subject areas
- Chemistry(all)
- Materials Science(all)
- Physics and Astronomy(all)
- Condensed Matter Physics
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In: Journal of Physics and Chemistry of Solids, Vol. 135, 109078, 12.2019.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Modulating optoelectronic properties of organo-metal halide perovskites with unsaturated heterocyclic cations via ring substitution
AU - Kevorkyants, R.
AU - Bahnemann, Detlef
AU - Emeline, Alexei V.
N1 - Funding Information: The authors acknowledge St. Petersburg State University's research grant (Pure ID 39054581 ). The authors also thank the Center for Computational Resources of St. Petersburg State University (Peterhof campus) for the provided CPU time.
PY - 2019/12
Y1 - 2019/12
N2 - We propose a ring substitution as a method of modulation of optoelectronic properties of organo-metal halide perovskites containing unsaturated heterocyclic cations. Periodic DFT calculations of tin trichloride perovskites with arizinium cation and its derivatives show that an introduction of the electron-withdrawing –C[tbnd]N and –F groups into azirinium ring stabilizes the materials' CBs formed from antibonding molecular π-orbitals of the ring. This leads to a decrease of the perovskite bandgaps as compared to that of the parent arizinium tin trichloride (1.06 eV). The effect of the electron-donating groups –CH 3 and –NH 2 on the materials’ CBs and bandgaps is opposite. The predicted bandgaps of the four perovskites cover the energy range of [0.52:1.93] eV. A combination of both electronic effects in one ring substituent allows for a finer tuning of the perovskite optoelectronic properties that is exemplified by fluorinated methylarizinium tin trichlorides. Bandgaps of these materials vary from 1.86 eV (R = -CH 3) to 1.17 eV (R = -CF 3). Thus, a ring substitution in unsaturated heterocyclic cations of organo-metal halide perovskites paves a way to modulating their optoelectronic properties in a wide energy range.
AB - We propose a ring substitution as a method of modulation of optoelectronic properties of organo-metal halide perovskites containing unsaturated heterocyclic cations. Periodic DFT calculations of tin trichloride perovskites with arizinium cation and its derivatives show that an introduction of the electron-withdrawing –C[tbnd]N and –F groups into azirinium ring stabilizes the materials' CBs formed from antibonding molecular π-orbitals of the ring. This leads to a decrease of the perovskite bandgaps as compared to that of the parent arizinium tin trichloride (1.06 eV). The effect of the electron-donating groups –CH 3 and –NH 2 on the materials’ CBs and bandgaps is opposite. The predicted bandgaps of the four perovskites cover the energy range of [0.52:1.93] eV. A combination of both electronic effects in one ring substituent allows for a finer tuning of the perovskite optoelectronic properties that is exemplified by fluorinated methylarizinium tin trichlorides. Bandgaps of these materials vary from 1.86 eV (R = -CH 3) to 1.17 eV (R = -CF 3). Thus, a ring substitution in unsaturated heterocyclic cations of organo-metal halide perovskites paves a way to modulating their optoelectronic properties in a wide energy range.
KW - DFT
KW - Electronic properties
KW - Optical absorption
KW - Organo-metal halide perovskites
UR - http://www.scopus.com/inward/record.url?scp=85068594021&partnerID=8YFLogxK
U2 - 10.1016/j.jpcs.2019.109078
DO - 10.1016/j.jpcs.2019.109078
M3 - Article
VL - 135
JO - Journal of Physics and Chemistry of Solids
JF - Journal of Physics and Chemistry of Solids
SN - 0022-3697
M1 - 109078
ER -