Lead-Free Semiconducting Organic–Inorganic Hybrid Perovskite with Mixed Organic Cations

Abstract

Hybrid perovskites with mixed organic cations have recently received extensive focus from researchers for their structural tunability, enhanced performance, and stability. However, because there are certain requirements for the size of different organic cations to form hybrid perovskites with mixed organic cations, reports on hybrid perovskites that can contain both phosphonium and ammonium cations have been rare. Here, we report an organic–inorganic hybrid perovskite (Me3PCH2CH2CH3)2(CH3CH2CH2NH3)Sb2Br9 (1) with [Me3PCH2CH2CH3]+ cations and [CH3CH2CH2NH3]+ cations. Compound 1 exhibits a reversible phase transition at 371.3/353.2 K. Compared with the organic–inorganic hybrid perovskites only with [Me3PCH2CH2CH3]+ cations or [CH3CH2CH2NH3]+ cations, the phase transition temperature of the organic–inorganic hybrid perovskite formed by mixing [Me3PCH2CH2CH3]+ cations and [CH3CH2CH2NH3]+ cations is significantly increased, and the thermal stability is improved. Structural analysis shows the disorder of [CH3CH2CH2NH3]+ cations and the twisting motion of [Me3PCH2CH2CH3]+ cations and the inorganic skeleton are the major reasons for the phase transition of 1 at high temperatures. Furthermore, 1 possesses semiconductor properties with an optical band gap of 2.945 eV. This discovery will shed light on exploring more excellent functional perovskite materials with mixed organic cations.

Synthesis and structure-dependent optical properties of two new organic–inorganic hybrid antimony(iii) chlorides

“…5,6 To tune the coordination geometries of metal ions and the connection modes of metal halide polyhedra, different organic molecules (e.g., amines, quaternary phosphonium salts, amino acids, and ionic liquids) have been adopted as structure-directing agents (SDAs). [7][8][9][10][11][12][13] Luo and co-workers reported the synthesis of the layered halide perovskite (R/S-PPA)EAPbBr 4 (PPA = 1-phenylpropylamine and EA = ethylammonium) with an excellent photoconductivity and robust polar photovoltage effect by alloying a small EA cation into the chained halide perovskite (R/S-PPA)PbBr 3 . 14 Kanatzidis and co-workers illustrated that the octahedral distortion and white-light emission in twodimensional (2D) lead bromides were strongly affected by the sizes and shapes of different amines intercalated within the halide perovskite layers.…”

A Lead‐Free Tin Organic‐Inorganic Hybrid Material with Reversible Phase Transition and Fluorescent Properties

“…[8,9] Therefore, they have several uses in a variety of industries, including solar cells, energy storage, [10] light detectors, optical communications, sensors, [11] and lasers. [12] For example, the two-dimensional hybrid perovskite (PFBA) 2 PbBr 4 combines the advantages of ease of fabrication and semiconductor performance to contribute to the field of multifunctional devices. [13] The organicinorganic hybrid material [Me 3 NCH 2 Cl]CdBrCl 2 with large piezoelectric coefficient has great application value in realizing electromechanical conversion.…”

“…Compared to typical inorganic phase change materials, organic‐inorganic hybrid mixtures combine the superior characteristics of organic molecules and inorganic substances, [7] such as phase change properties, optical properties, electrical properties, mechanical and thermal stability, and structural and functional diversity [8,9] . Therefore, they have several uses in a variety of industries, including solar cells, energy storage, [10] light detectors, optical communications, sensors, [11] and lasers [12] . For example, the two‐dimensional hybrid perovskite (PFBA) 2 PbBr 4 combines the advantages of ease of fabrication and semiconductor performance to contribute to the field of multifunctional devices [13] .…”

Hybrid Perovskite Molecular Rotor Ferroelastic Semiconductor Constructed by Supramolecular Assembly

“…These shortcomings hinder its further application and development. At present, organic–inorganic hybrid perovskites composed of organic and inorganic components have the advantages of simple processing, low cost, easy film preparation, and environmental friendliness. − They provide a new platform for multifunctional applications, such as actuators, morphological memory, capacitors, semiconductor photoelectric detectors, etc. − However, it is important to note that ferroelastics involve a symmetry-breaking and structural phase transition (SPT). , Therefore, the development of ferroelastic materials is still limited.…”