TY - JOUR

T1 - Modulating optoelectronic properties of organo-metal halide perovskites with unsaturated heterocyclic cations via ring substitution

AU - Kevorkyants, R.

AU - Bahnemann, D. W.

AU - Emeline, A. V.

PY - 2019/12/1

Y1 - 2019/12/1

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 –CH3 and –NH2 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 = -CH3) to 1.17 eV (R = -CF3). 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 –CH3 and –NH2 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 = -CH3) to 1.17 eV (R = -CF3). 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

KW - CSPBCL3

KW - LEAD

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

AN - SCOPUS:85068594021

VL - 135

JO - Journal of Physics and Chemistry of Solids

JF - Journal of Physics and Chemistry of Solids

SN - 0022-3697

M1 - 109078

ER -