Zero-Dimensional Lead-Free Hybrid Perovskite-like Material with a Quantum-Well Structure

Abstract

Low-dimensional perovskites are an emerging class of materials with high stability and excellent optoelectronic properties. Herein, we introduce a novel, lead-free, zero-dimensional perovskite-like material, (1,3-propanediammonium) 2 Bi 2 I 10 •2H 2 O, for optoelectronic applications. This material exhibited good moisture and thermal stability under ambient conditions. Single-crystal X-ray diffraction analysis revealed a quantum-well structure having the inorganic Bi 2 I 10 4− clusters periodically arranged in the crystallographic "c" axis separated by a distance of 5.36 Å, sandwiched by independent layers of organic cations. The density functional theory calculations showed that the oxygen in water molecules has a significant contribution to the band edges of the material. The photodetector device fabricated using this material showed an efficient charge separation at low voltage (1 V) due to the good electronic conduction between the Bi 2 I 10 4− dimer units.H ybrid perovskites have emerged as a unique semiconductor material for various optoelectronic device applications during the past few years. 1−3 Excellent properties such as long charge carrier diffusion length, low exciton binding energy, facile band gap tunability, and low-temperature solution processability made this material highly useful in these devices. 4−7 Nevertheless, poor stability under ambient conditions and toxicity of lead hampers their commercial usage. 8,9 Reports suggest that lower dimensional perovskites exhibit moisture tolerance to a great extent. 10−13 In order to address the toxicity issue, less toxic metal ions, such as Sn 2+ , Bi 3+ , Sb 3+ , and so forth, having ns 2 electrons similar to Pb 2+ were introduced into the perovskite structure. 14−16 Among them, tin-based materials are highly unstable due to the facile oxidation of the Sn 2+ to Sn 4+ state. 17 On the other hand, bismuth-and antimony-based zero-dimensional perovskites exhibited excellent moisture stability due to their rigid M 2 X 9 3−

Lead-Free Perovskites for Lighting and Lasing Applications: A Minireview

“…As for the lead-based, lead-free perovskites can also be divided to organic–inorganic and all-inorganic. For organic–inorganic lead-free perovskites, standard methylammonium [39,40,50], butylamine [32], 1,3-propanediammonium [51], and phenethylammonium [52] can be used as the A cations. For all-inorganic lead-free perovskites, the most used A cation is Cs, however there are several reports on Rb and Rb/Cs mixture [29,37].…”

“…Also due to the presence of a hydrophobic organic chain, it was shown that the (C 6 H 5 NH 3 )BiI 4 perovskite can withstand constant exposure of moisture for one year in ambient. Among the organic–inorganic bismuth-based perovskites, a (1,3-propanediammonium) 2 Bi 2 I 10 ·2H 2 O with quantum-well morphology can be highlighted [51]. This material has sandwich structure with the inorganic Bi 2 I 10 4− clusters periodically arranged in the crystallographic “c” axis separated by 0.5 nm layers of organic cations.…”

Rigid Amine‐Induced Pseudo‐3 D Lead‐Free Bismuth Halide Perovskite with an Improved Band Edge for Visible‐Light Absorption

“…Interestingly, the small band gap of 1.48 eV was comparable to that of (CH 3 NH 3 )PbI 3 , and very close to the ideal band gap . The band gaps of organometal halide perovskites depend on a wide range of factors, including the halogen, the connectivity of the inorganic part, special orbital interaction, and even quantum‐well structure . Compared with 2 , the small band gap of 1 could be owing to the different halogens in the structure.…”

“…By introducing organic amines at the A sites in the A a Bi b X a +3 b family, Bi‐based perovskites with different structures have been synthesized (Table ). The optical band gaps can be tuned by changing the halides, according to the sequence Cl>Br>I . Most of the materials have normal 0 D and 1 D inorganic components.…”

Halogen Substitution in Zero‐Dimensional Mixed Metal Halides toward Photoluminescence Modulation and Enhanced Quantum Yield

“…Zero‐dimensional (0D) organic−inorganic hybrid metal halides belong to a class of emerging optoelectronic materials with unique host−guest structures, suggesting large potentials in photodetectors, [ 1 ] white‐light emitting diodes (WLEDs), [ 2 ] X‐ray scintillations, [ 3 ] luminescent sensors, [ 4 ] etc. It is noteworthy that 0D here is defined as the molecular level concept, in which the not‐networked individual metal halide units or clusters act as a judging criteria for this type of materials.…”