TY - JOUR

T1 - Polymeric iodobismuthates {[Bi 3 I 10 ]} and {[BiI 4 ]} with N-heterocyclic cations

T2 - Promising perovskite-like photoactive materials for electronic devices

AU - Usoltsev, Andrey N.

AU - Elshobaki, Moneim

AU - Adonin, Sergey A.

AU - Frolova, Lyubov A.

AU - Derzhavskaya, Tatiyana

AU - Abramov, Pavel A.

AU - Anokhin, Denis V.

AU - Korolkov, Ilya V.

AU - Luchkin, Sergey Yu

AU - Dremova, Nadezhda N.

AU - Stevenson, Keith J.

AU - Sokolov, Maxim N.

AU - Fedin, Vladimir P.

AU - Troshin, Pavel A.

N1 - Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019/3/21

Y1 - 2019/3/21

N2 - A screening of the reactions between BiI 3 and iodide salts of different N-alkylated heterocycles (pyridine, quinoline, isoquinoline) resulted in the preparation and structural characterization of six novel iodobismuthate complexes, including two compounds exhibiting an unprecedented {[Bi 3 I 10 ]} polymeric moiety. It has been shown that the chemical composition and structure of the iodobismuthates significantly affect their optical and electronic properties. In particular, the narrowest band gaps (E g ) were revealed by {[Bi 3 I 10 ]} iodobismuthates, while the compounds incorporating {[BiI 4 ]} polymeric frameworks showed 0.2-0.3 eV wider E g . GIXRD analysis evidenced that all three iodobismuthates investigated in thin films show mainly the horizontal (parallel to the substrate) orientation of the 1D polymeric Bi-I frameworks. Such arrangement blocks the charge transport in vertical direction (orthogonal to the substrate) since the conductive Bi-I chains are separated with insulating bulky organic cations. As a consequence, standard planar junction solar cells based on new iodobismuthates revealed low power conversion efficiencies approaching 0.12% only. However, strong in-plane photoconductivity observed for iodobismuthates enabled the fabrication of efficient planar photodetectors, which paves a way to the practical use of this exotic family of materials. Most importantly, the presented systematic study revealed the most general guidelines for future rational design of perovskite-like materials for emerging generation of environment-friendly perovskite photovoltaics emphasizing the importance of the isotropic charge transport in the films of 3D materials and achieving proper orientation of 1D and 2D frameworks with respect to the charge collecting electrodes in anisotropic low dimensional systems.

AB - A screening of the reactions between BiI 3 and iodide salts of different N-alkylated heterocycles (pyridine, quinoline, isoquinoline) resulted in the preparation and structural characterization of six novel iodobismuthate complexes, including two compounds exhibiting an unprecedented {[Bi 3 I 10 ]} polymeric moiety. It has been shown that the chemical composition and structure of the iodobismuthates significantly affect their optical and electronic properties. In particular, the narrowest band gaps (E g ) were revealed by {[Bi 3 I 10 ]} iodobismuthates, while the compounds incorporating {[BiI 4 ]} polymeric frameworks showed 0.2-0.3 eV wider E g . GIXRD analysis evidenced that all three iodobismuthates investigated in thin films show mainly the horizontal (parallel to the substrate) orientation of the 1D polymeric Bi-I frameworks. Such arrangement blocks the charge transport in vertical direction (orthogonal to the substrate) since the conductive Bi-I chains are separated with insulating bulky organic cations. As a consequence, standard planar junction solar cells based on new iodobismuthates revealed low power conversion efficiencies approaching 0.12% only. However, strong in-plane photoconductivity observed for iodobismuthates enabled the fabrication of efficient planar photodetectors, which paves a way to the practical use of this exotic family of materials. Most importantly, the presented systematic study revealed the most general guidelines for future rational design of perovskite-like materials for emerging generation of environment-friendly perovskite photovoltaics emphasizing the importance of the isotropic charge transport in the films of 3D materials and achieving proper orientation of 1D and 2D frameworks with respect to the charge collecting electrodes in anisotropic low dimensional systems.

KW - SOLAR-CELLS

KW - LEAD-FREE

KW - CRYSTAL-STRUCTURES

KW - OPTICAL-PROPERTIES

KW - LOW-TEMPERATURE

KW - SOLID-STATE

KW - THIN-FILMS

KW - HYBRID

KW - EFFICIENT

KW - COMPLEXES

UR - http://www.scopus.com/inward/record.url?scp=85062874593&partnerID=8YFLogxK

U2 - 10.1039/c8ta09204d

DO - 10.1039/c8ta09204d

M3 - Article

AN - SCOPUS:85062874593

VL - 7

SP - 5957

EP - 5966

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 11

ER -