Crystal and Band-Gap Engineering of One-Dimensional Antimony/Bismuth-Based Organic-Inorganic Hybrids.

Hybrid halide perovskites are emerging semiconducting materials with a diverse set of remarkable optoelectronic properties. Besides the widely studied lead halide perovskites, Pb-free metal halides such as Bi- and Sb-containing hybrid organic-inorganic materials have shown potential as semiconductors and have been deemed candidates for optoelectronic devices. Here, we report a series of 1D Sb/Bi-based organic-inorganic hybrid alloys: [4ApyH]SbxBi1-xIyBr4-y, where 4ApyH stands for the 4-aminopyridine cations. These compounds are assembled by edge-sharing octahedral [MX6] units stabilizing 1D chains with organic cations filled in between. The crystallographic data of eight selected complexes show that [4ApyH]SbxBi1-xIyBr4-y has at least five phases (space group) with the difference metal and halogen content: Pbca ([4ApyH]BiI4), Pca21 ([4ApyH]Sb0.5Bi0.5I4), P21/c ([4ApyH]SbI4 (100 K), [4ApyH]BiI2Br2, [4ApyH]BiBr4, and [4ApyH]SbBr4 (100 K)), I2/a ([4ApyH]Sb0.5Bi0.5I2Br2and [4ApyH]SbI2Br2), and C2/c ([4ApyH]SbI4 (298 K) and [4ApyH]SbBr4 (298 K)). Powder X-ray diffraction shows that the phase of the sample changes with a change of the metal and halogen ratios, and the change law accords with Vegard's law. The optical band gaps are heavily affected by the metal and halide contents, ranging from 1.94 eV for [4ApyH]BiI4 to 2.73 eV for [4ApyH]SbBr4. When Sb substitutes for Bi to form an alloy, the band gap increases from 1.94 for [4ApyH]BiI4 to 1.67 eV for [4ApyH]SbI4, from 2.13 eV for [4ApyH]BiI2Br2 to 2.41 eV for [4ApyH]SbI2Br2, and from 2.55 eV for [4ApyH]BiBr4 to 2.73 eV for [4ApyH]SbBr4. The conductivity of [4ApyH]SbxBi1-xI4 increased from ∼1.00 × 10-15 to 2.14 × 10-8 S cm-1 with an increase of the Sb content. Solution-deposited thin films of the nine complexes show the same (110) orientation, displaying a parallel growth orientation with respect to the substrate. The devices of [4ApyH]Sb0.8Bi0.2I4 and [4ApyH]SbI4 demonstrated stable open-circuit photovoltages of 0.55 and 0.44 V, steady-state short-circuit photocurrent densities of 1.52 and 1.81 mA cm-2, and light-to-electrical energy conversion efficiencies of 0.29% and 0.30%, respectively.

Tracking the dimensional conversion process of semiconducting lead bromide perovskites by mass spectroscopy, powder X-ray diffraction, microcalorimetry and crystallography.

The structural information of a material in both the solid state and solution state is essential to the in-depth understanding of the properties of inorganic-organic hybrid materials. A one-dimensional (1D) lead bromide formulated as [H][NH3(CH2)2SS(CH2)2NH3][H2O][PbBr5] (1) could be converted into a new two-dimensional (2D) complex, [NH3(CH2)2SS(CH2)2NH3][PbBr4] (2), by soaking the crystals in water. The isolated 2D compound showed single-layer lead-halide perovskite structures. Electrospray ionization mass spectrometry (ESI-MS) analyses of the reaction solution revealed that the [PbBr3]- fragments are initially formed from the rapid decomposition of the 1D [PbBr5]3- chains and subsequently reassemble into 2D [PbBr4]2- layers, which was verified by powder X-ray diffraction (PXRD) and microcalorimetry. Because of the decomposition and reassembly process, complex 1 could be used as a precursor to synthesize M2+-doped 2D lead bromide perovskites, namely, Mn@2, Ni@2 and Cd@2. In addition, preliminary tests indicated that complex 2 exhibited a lower optical band gap (3.25 eV) and higher electrical conductivity (3.2 × 10-11 S cm-1) than complex 1 (3.38 eV, 5.4 × 10-12 S cm-1).

Monodisperse Bismuth-Halide Double Perovskite Nanocrystals Confined in Mesoporous Silica Templates.

Metal halide perovskites have fascinating electronic properties and have already been implemented in various devices. Although the behavior of the properties of lead halide perovskite nanocrystals has been studied, the properties of lead-free perovskite nanocrystals are less well-understood because synthesizing them is still very challenging. Here, a simple and popularizable method has been demonstrated to grow monodisperse bismuth-halide double perovskite nanocrystals, Cs2AgBiBr6 (1), inside three kinds of mesoporous silica templates. The size and morphology of nanocrystals depend on the structure and pore size of the template. Structural analysis shows that the nanocrystals of various sizes and morphologies retain the crystal structure of bimetallic perovskite. 1 exhibits different morphologies in the silicon channels of three templates: square nanoparticles in KIT-6, spherical and rodlike particles in SBA-15, and nanowires in MCM-41. UV-vis-NIR and photoluminescence measurements show us the variation of band gap and carrier recombination time due to quantum confinement of nanocrystals in mesoporous silicon materials. The band gaps of nanocrystals in the template exhibit an obvious blue shift compared with that of the bulk sample, and the carrier recombination time is significantly shortened. We show that mesoporous silicon templates can be used to prepare lead-free perovskite nanocrystals, and the controllable preparation of nanocrystals can be achieved by the template's own characteristics. This provides a new idea for us to find new functional materials of lead-free metal halide solid-state light-emitting diodes.